Heat transfer compositions

ABSTRACT

The invention provides a heat transfer composition comprising (i) a first component selected from trans-1,3,3,3-tetrafluoropropene (R-1234ze(E)), cis-1,3,3,3-tetrafluoropropene (R-1234ze(Z)) and mixtures thereof; (ii) carbon dioxide (R-744); and (iii) a third component selected from 2,3,3,3-tetrafluoropropene (R-1234yf), 3,3,3-trifluoropropene (R-1243zf), and mixtures thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is the U.S. National Phase under 35 U.S.C. §371 ofInternational Application No. PCT/GB2011/000771, filed May 20, 2011,designating the United States and published in English on Nov. 24, 2011,as WO 2011/144908, which claims priority to United Kingdom ApplicationNo. 1008438.2, filed May 20, 2010, United Kingdom Application No.1010057.6, filed Jun. 16, 2010, United Kingdom Application No.1020624.1, filed Dec. 6, 2010, and United Kingdom Application No.1102556.6, filed Feb. 14, 2011, each of which is incorporated byreference in its entirety.

FIELD

The invention relates to heat transfer compositions, and in particularto heat transfer compositions which may be suitable as replacements forexisting refrigerants such as R-134a, R-152a, R-1234yf, R-22, R-410A,R-407A, R-407B, R-407C, R507 and R-404a.

BACKGROUND

The listing or discussion of a prior-published document or anybackground in the specification should not necessarily be taken as anacknowledgement that a document or background is part of the state ofthe art or is common general knowledge.

Mechanical refrigeration systems and related heat transfer devices suchas heat pumps and air-conditioning systems are well known. In suchsystems, a refrigerant liquid evaporates at low pressure taking heatfrom the surrounding zone. The resulting vapour is then compressed andpassed to a condenser where it condenses and gives off heat to a secondzone, the condensate being returned through an expansion valve to theevaporator, so completing the cycle. Mechanical energy required forcompressing the vapour and pumping the liquid is provided by, forexample, an electric motor or an internal combustion engine.

In addition to having a suitable boiling point and a high latent heat ofvaporisation, the properties preferred in a refrigerant include lowtoxicity, non-flammability, non-corrosivity, high stability and freedomfrom objectionable odour. Other desirable properties are readycompressibility at pressures below 25 bars, low discharge temperature oncompression, high refrigeration capacity, high efficiency (highcoefficient of performance) and an evaporator pressure in excess of 1bar at the desired evaporation temperature.

Dichlorodifluoromethane (refrigerant R-12) possesses a suitablecombination of properties and was for many years the most widely usedrefrigerant. Due to international concern that fully and partiallyhalogenated chlorofluorocarbons were damaging the earth's protectiveozone layer, there was general agreement that their manufacture and useshould be severely restricted and eventually phased out completely. Theuse of dichlorodifluoromethane was phased out in the 1990's.

Chlorodifluoromethane (R-22) was introduced as a replacement for R-12because of its lower ozone depletion potential. Following concerns thatR-22 is a potent greenhouse gas, its use is also being phased out.

Whilst heat transfer devices of the type to which the present inventionrelates are essentially closed systems, loss of refrigerant to theatmosphere can occur due to leakage during operation of the equipment orduring maintenance procedures. It is important, therefore, to replacefully and partially halogenated chlorofluorocarbon refrigerants bymaterials having zero ozone depletion potentials.

In addition to the possibility of ozone depletion, it has been suggestedthat significant concentrations of halocarbon refrigerants in theatmosphere might contribute to global warming (the so-called greenhouseeffect). It is desirable, therefore, to use refrigerants which haverelatively short atmospheric lifetimes as a result of their ability toreact with other atmospheric constituents such as hydroxyl radicals, oras a result of ready degradation through photolytic processes.

R-410A and R-407 refrigerants (including R-407A, R-407B and R-407C) havebeen introduced as a replacement refrigerant for R-22. However, R-22,R-410A and the R-407 refrigerants all have a high global warmingpotential (GWP, also known as greenhouse warming potential).

1,1,1,2-tetrafluoroethane (refrigerant R-134a) was introduced as areplacement refrigerant for R-12. R-134a is an energy efficientrefrigerant, used currently for automotive air conditioning. However itis a greenhouse gas with a GWP of 1430 relative to CO₂ (GWP of CO₂ is 1by definition). The proportion of the overall environmental impact ofautomotive air conditioning systems using this gas, which may beattributed to the direct emission of the refrigerant, is typically inthe range 10-20%. Legislation has now been passed in the European Unionto rule out use of refrigerants having GWP of greater than 150 for newmodels of car from 2011. The car industry operates global technologyplatforms, and in any event emission of greenhouse gas has globalimpact, thus there is a need to find fluids having reduced environmentalimpact (e.g. reduced GWP) compared to HFC-134a.

R-152a (1,1-difluoroethane) has been identified as an alternative toR-134a. It is somewhat more efficient than R-134a and has a greenhousewarming potential of 120. However the flammability of R-152a is judgedtoo high, for example to permit its safe use in mobile air conditioningsystems. In particular it is believed that its lower flammable limit inair is too low, its flame speeds are too high, and its ignition energyis too low.

Thus there is a need to provide alternative refrigerants having improvedproperties such as low flammability. Fluorocarbon combustion chemistryis complex and unpredictable. It is not always the case that mixing anon-flammable fluorocarbon with a flammable fluorocarbon reduces theflammability of the fluid or reduces the range of flammable compositionsin air. For example, the inventors have found that if non-flammableR-134a is mixed with flammable R-152a, the lower flammable limit of themixture alters in a manner which is not predictable. The situation isrendered even more complex and less predictable if ternary or quaternarycompositions are considered.

There is also a need to provide alternative refrigerants that may beused in existing devices such as refrigeration devices with little or nomodification.

R-1234yf (2,3,3,3-tetrafluoropropene) has been identified as a candidatealternative refrigerant to replace R-134a in certain applications,notably the mobile air conditioning or heat pumping applications. ItsGWP is about 4. R-1234yf is flammable but its flammabilitycharacteristics are generally regarded as acceptable for someapplications including mobile air conditioning or heat pumping. Inparticular, when compared with R-152a, its lower flammable limit ishigher, its minimum ignition energy is higher and the flame speed in airis significantly lower than that of R-152a.

The environmental impact of operating an air conditioning orrefrigeration system, in terms of the emissions of greenhouse gases,should be considered with reference not only to the so-called “direct”GWP of the refrigerant, but also with reference to the so-called“indirect” emissions, meaning those emissions of carbon dioxideresulting from consumption of electricity or fuel to operate the system.Several metrics of this total GWP impact have been developed, includingthose known as Total Equivalent Warming Impact (TEWI) analysis, orLife-Cycle Carbon Production (LCCP) analysis. Both of these measuresinclude estimation of the effect of refrigerant GWP and energyefficiency on overall warming impact. Emissions of carbon dioxideassociated with manufacture of the refrigerant and system equipmentshould also be considered.

The energy efficiency and refrigeration capacity of R-1234yf have beenfound to be significantly lower than those of R-134a and in addition thefluid has been found to exhibit increased pressure drop in systempipework and heat exchangers. A consequence of this is that to useR-1234yf and achieve energy efficiency and cooling performanceequivalent to R-134a, increased complexity of equipment and increasedsize of pipework is required, leading to an increase in indirectemissions associated with equipment. Furthermore, the production ofR-1234yf is thought to be more complex and less efficient in its use ofraw materials (fluorinated and chlorinated) than R-134a. Currentprojections of long term pricing for R-1234yf is in the range 10-20times greater than R-134a. This price differential and the need forextra expenditure on hardware will limit the rate at which refrigerantsare changed and hence limit the rate at which the overall environmentalimpact of refrigeration or air conditioning may be reduced. In summary,the adoption of R-1234yf to replace R-134a will consume more rawmaterials and result in more indirect emissions of greenhouse gases thandoes R-134a.

Some existing technologies designed for R-134a may not be able to accepteven the reduced flammability of some heat transfer compositions (anycomposition having a GWP of less than 150 is believed to be flammable tosome extent).

SUMMARY

A principal object of the present invention is therefore to provide aheat transfer composition which is usable in its own right or suitableas a replacement for existing refrigeration usages which should have areduced GWP, yet have a capacity and energy efficiency (which may beconveniently expressed as the “Coefficient of Performance”) ideallywithin 10% of the values, for example of those attained using existingrefrigerants (e.g. R-134a, R-152a, R-1234yf, R-22, R-410A, R-407A,R-407B, R-407C, R507 and R-404a), and preferably within less than 10%(e.g. about 5%) of these values. It is known in the art that differencesof this order between fluids are usually resolvable by redesign ofequipment and system operational features. The composition should alsoideally have reduced toxicity and acceptable flammability.

The subject invention addresses the above deficiencies by the provisionof a heat transfer composition comprising (i) a first component selectedfrom trans-1,3,3,3-tetrafluoropropene (R-1234ze(E)),cis-1,3,3,3-tetrafluoropropene (R-1234ze(Z)) and mixtures thereof; (ii)carbon dioxide (CO₂ or R-744); and (iii) a third component selected from2,3,3,3-tetrafluoropropene (R-1234yf), 3,3,3-trifluoropropene (R-1243zf)and mixtures thereof.

All of the chemicals herein described are commercially available. Forexample, the fluorochemicals may be obtained from Apollo Scientific(UK).

Typically, the compositions of the invention containtrans-1,3,3,3-tetrafluoropropene (R-1234ze(E)). The majority of thespecific compositions described herein contain R-1234ze(E). It is to beunderstood, of course, that some or all of the R-1234ze(E) in suchcompositions can be replaced by R-1234ze(Z). The trans isomer iscurrently preferred, however.

Typically, the composition of the invention contain at least about 5% byweight R-1234ze(E), preferably at least about 15% by weight. In oneembodiment, the compositions of the invention contain at least about 45%by weight R-1234ze(E), for example from about 50 to about 98% by weight.

The preferred amounts and choice of components for the invention aredetermined by a combination of properties:

-   -   (a) Flammability: non-flammable or weakly flammable compositions        are preferred.    -   (b) Effective operating temperature of the refrigerant in an air        conditioning system evaporator.    -   (c) Temperature “glide” of the mixture and its effect on heat        exchanger performance.    -   (d) Critical temperature of the composition. This should be        higher than the maximum expected condenser temperature.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of heating COP of CO₂/R1234yf/R1234ze(E) mixtures as afunction of CO₂ content of mixture; and

FIG. 2 is a graph of heating capacity of CO₂/R1234yf/R1234ze(E) mixturesas a function of CO₂ content of mixture.

DETAILED DESCRIPTION

The effective operating temperature in an air conditioning cycle,especially automotive air conditioning, is limited by the need to avoidice formation on the air-side surface of the refrigerant evaporator.Typically air conditioning systems must cool and dehumidify humid air;so liquid water will be formed on the air-side surface. Most evaporators(without exception for the automotive application) have finned surfaceswith narrow fin spacing. If the evaporator is too cold then ice can beformed between the fins, restricting the flow of air over the surfaceand reducing overall performance by reducing the working area of theheat exchanger.

It is known for automotive air-conditioning applications (ModernRefrigeration and Air Conditioning by AD Althouse et al, 1988 edition,Chapter 27, which is incorporated herein by reference) that refrigerantevaporation temperatures of −2° C. or higher are preferred to ensurethat the problem of ice formation is thereby avoided.

It is also known that non-azeotropic refrigerant mixtures exhibittemperature “glide” in evaporation or condensation. In other words, asthe refrigerant is progressively vaporised or condensed at constantpressure, the temperature rises (in evaporation) or drops (incondensation), with the total temperature difference (inlet to outlet)being referred to as the temperature glide. The effect of glide onevaporation and condensation temperature must also be considered.

The critical temperature of a heat transfer composition should be higherthan the maximum expected condenser temperature. This is because thecycle efficiency drops as critical temperature is approached. As thishappens, the latent heat of the refrigerant is reduced and so more ofthe heat rejection in the condenser takes place by cooling gaseousrefrigerant; this requires more area per unit heat transferred.

R-410A is commonly used in building and domestic heat pump systems andby way of illustration its critical temperature of about 71° C. ishigher than the highest normal condensing temperature required todeliver useful warm air at about 50° C. The automotive duty requires airat about 50° C. so the critical temperature of the fluids of theinvention should be higher than this if a conventional vapourcompression cycle is to be utilised. Critical temperature is preferablyat least 15K higher than the maximum air temperature.

In one aspect, the compositions of the invention have a criticaltemperature of greater than about 65° C., preferably greater than about70° C.

The carbon dioxide content of the compositions of the invention islimited primarily by considerations (b) and/or (c) and/or (d) above.Conveniently, the compositions of the invention typically contain up toabout 35% by weight R-744, preferably up to about 30% by weight.

In a preferred aspect, the compositions of the invention contain fromabout 4 to about 30% R-744 by weight, preferably from about 4 to about28% by weight, or from about 8 to about 30% by weight, or from about 10to about 30% by weight.

The content of the third component, which may include flammablerefrigerants such as R-1234yf is selected so that even in the absence ofthe carbon dioxide element of the composition, the residual fluorocarbonmixture has a lower flammable limit in air at ambient temperature (e.g.23° C.) (as determined in the ASHRAE-34 12 liter flask test apparatus)which is greater than 5% v/v, preferably greater than 6% v/v, mostpreferably such that the mixture is non-flammable. The issue offlammability is discussed further later in this specification.

Typically, the compositions of the invention contain up to about 60% byweight of the third component. Preferably, the compositions of theinvention contain up to about 50% by weight of the third component.Conveniently, the compositions of the invention contain up to about 45%by weight of the third component. In one aspect, the compositions of theinvention contain from about 1 to about 40% by weight of the thirdcomponent.

In one embodiment, the compositions of the invention comprise from about10 to about 95% R-1234ze(E) by weight, from about 2 to about 30% byweight R-744, and from about 3 to about 60% by weight of the thirdcomponent.

As used herein, all % amounts mentioned in compositions herein,including in the claims, are by weight based on the total weight of thecompositions, unless otherwise stated.

For the avoidance of doubt, it is to be understood that the stated upperand lower values for ranges of amounts of components in the compositionsof the invention described herein may be interchanged in any way,provided that the resulting ranges fall within the broadest scope of theinvention.

In one embodiment, the compositions of the invention consist essentiallyof (or consist of) the first component (e.g. R-1234ze(E)), R-744 and thethird component.

By the term “consist essentially of”, we mean that the compositions ofthe invention contain substantially no other components, particularly nofurther (hydro)(fluoro) compounds (e.g. (hydro)(fluoro)alkanes or(hydro)(fluoro)alkenes) known to be used in heat transfer compositions.We include the term “consist of” within the meaning of “consistessentially of”.

For the avoidance of doubt, any of the compositions of the inventiondescribed herein, including those with specifically defined compoundsand amounts of compounds or components, may consist essentially of (orconsist of) the compounds or components defined in those compositions.

The third component is selected from R-1234yf, R-1243zf, and mixturesthereof.

In one aspect, the third component contains only one of the listedcomponents. For example, the third component may contain only one ofR-1234yf or R-1243zf. Thus, the compositions of the invention may beternary blends of R-1234ze(E), R-744 and one of the listed thirdcomponents (e.g. R-1234yf or R-1243zf).

However, mixtures of R-1234yf and R-1243zf can be used as the thirdcomponent.

The invention contemplates compositions in which additional compoundsare included in the third component. Example of such compounds includedifluoromethane (R-32), 1,1-difluoroethane (R-152a), fluoroethane(R-161), 1,1,1,2-tetrafluoroethane (R-134a), 1,1,1-trifluoropropane(R-263fb), 1,1,1,2,3-pentafluoropropane (R-245eb), propylene (R-1270),propane (R-290), n-butane (R-600), isobutane (R-600a), ammonia (R-717)and mixtures thereof.

For example, the compositions of the invention may include R-134a. Ifpresent, the R-134a typically is present in an amount of from about 2 toabout 50% by weight, such as from about 5 to about 40% by weight (e.g.from about 5 to about 20% by weight).

Preferably, the compositions of the invention which contain R-134a arenon-flammable at a test temperature of 60° C. using the ASHRAE-34methodology. Advantageously, the mixtures of vapour that exist inequilibrium with the compositions of the invention at any temperaturebetween about −20° C. and 60° C. are also non-flammable.

In one embodiment, the third component comprises R-1234yf. The thirdcomponent may consist essentially of (or consist of) R-1234yf.

Compositions of the invention which contain R-1234yf typically containit in an amount of from about 2 to about 60% by weight, for instanceabout 4 to about 50% by weight. Conveniently the R-1243yf is present inan amount of from about 6 to about 40%.

Preferred compositions of the invention contain from about 10 to about92% R-1234ze(E), from about 4 to about 30% by weight R-744 and fromabout 4 to about 60% by weight R-1234yf. For example, such compositionsmay comprise from about 22 to about 84% R-1234ze(E), from about 10 toabout 28% by weight R-744 and from about 6 to about 50% by weightR-1234yf.

Further preferred compositions of the invention contain from about 14 toabout 86% R-1234ze(E), from about 4 to about 26% by weight R-744 andfrom about 10 to about 60% by weight R-1234yf.

Another group of compositions of the invention containing R-1234yfcomprise from about 32 to about 88% R-1234ze(E), from about 8 to about28% by weight R-744 and from about 4 to about 40% by weight R-1234yf.

In one embodiment, the third component comprises R-1243zf. The thirdcomponent may consist essentially of (or consist of) R-1243zf.

Compositions of the invention which contain R-1243zf typically containit in an amount of from about 2 to about 60% by weight, for instanceabout 4 to about 50% by weight. Conveniently the R-1243zf is present inan amount of from about 6 to about 40%.

Preferred compositions of the invention contain from about 20 to about92% R-1234ze(E), from about 4 to about 30% by weight R-744 and fromabout 4 to about 50% by weight R-1243zf. For example, such compositionsmay comprise from about 32 to about 88% R-1234ze(E), from about 6 toabout 28% by weight R-744 and from about 6 to about 40% by weightR-1243zf.

Further advantageous compositions of the invention contain from about 25to about 91% R-1234ze(E), from about 4 to about 30% by weight R-744 andfrom about 5 to about 45% by weight R-1243zf. For example, suchcompositions may contain from about 27 to about 85% by weightR-1234ze(E), from about 10 to about 28% by weight R-744 and from about 5to about 45% by weight R-1243zf.

The compositions of the invention may further contain pentafluoroethane(R-125). If present, R-125 typically is present in amounts up to about40% by weight, preferably from about 2 to about 20% by weight.

Compositions according to the invention conveniently comprisesubstantially no R-1225 (pentafluoropropene), conveniently substantiallyno R-1225ye (1,2,3,3,3-pentafluoropropene) or R-1225zc(1,1,3,3,3-pentafluoropropene), which compounds may have associatedtoxicity issues.

By “substantially no”, we include the meaning that the compositions ofthe invention contain 0.5% by weight or less of the stated component,preferably 0.1% or less, based on the total weight of the composition.

Certain compositions of the invention may contain substantially no:

-   -   (i) 2,3,3,3-tetrafluoropropene (R-1234yf),    -   (ii) cis-1,3,3,3-tetrafluoropropene (R-1234ze(Z)), and/or    -   (iii) 3,3,3-trifluoropropene (R-1243zf).

The compositions of the invention have zero ozone depletion potential.

Typically, the compositions of the invention have a GWP that is lessthan 1300, preferably less than 1000, more preferably less than 800,500, 400, 300 or 200, especially less than 150 or 100, even less than 50in some cases. Unless otherwise stated, IPCC (Intergovernmental Panel onClimate Change) TAR (Third Assessment Report) values of GWP have beenused herein.

Advantageously, the compositions are of reduced flammability hazard whencompared to the third component(s) alone, e.g. R-1234yf or R-1243zf.Preferably, the compositions are of reduced flammability hazard whencompared to R-1234yf.

In one aspect, the compositions have one or more of (a) a higher lowerflammable limit; (b) a higher ignition energy; or (c) a lower flamevelocity compared to the third component(s) such as R-1234yf orR-1243zf. In a preferred embodiment, the compositions of the inventionare non-flammable. Advantageously, the mixtures of vapour that exist inequilibrium with the compositions of the invention at any temperaturebetween about −20° C. and 60° C. are also non-flammable.

Flammability may be determined in accordance with ASHRAE Standard 34incorporating the ASTM Standard E-681 with test methodology as perAddendum 34p dated 2004, the entire content of which is incorporatedherein by reference.

In some applications it may not be necessary for the formulation to beclassed as non-flammable by the ASHRAE-34 methodology; it is possible todevelop fluids whose flammability limits will be sufficiently reduced inair to render them safe for use in the application, for example if it isphysically not possible to make a flammable mixture by leaking therefrigeration equipment charge into the surrounds.

R-1234ze(E) is non-flammable in air at 23° C., although it exhibitsflammability at higher temperatures in humid air. We have determined byexperimentation that mixtures of R-1234ze(E) with flammablefluorocarbons such as R-32, R-152a or R-161 will remain non-flammable inair at 23° C. if the “fluorine ratio” R_(f) of the mixture is greaterthan about 0.57, where R_(f) is defined per gram-mole of the overallrefrigerant mixture as:R _(f)=(gram-moles of fluorine)/(gram-moles fluorine+gram-moleshydrogen)

Thus for R-161, R_(f)=1/(1+5)=1/6 (0.167) and it is flammable, incontrast R-1234ze(E) has R_(f)=4/6 (0.667) and it is non-flammable. Wefound by experiment that a 20% v/v mixture of R-161 in R-1234ze(E) wassimilarly non-flammable. The fluorine ratio of this non-flammablemixture is 0.2*(1/6)+0.8*(4/6)=0.567.

The validity of this relationship between flammability and fluorineratio of 0.57 or higher has thusfar been experimentally proven forHFC-32, HFC-152a and mixtures of HFC-32 with HFC-152a.

Takizawa et al, Reaction Stoichiometry for Combustion of FluoroethaneBlends, ASHRAE Transactions 112(2) 2006 (which is incorporated herein byreference), shows that there exists a near-linear relationship betweenthis ratio and the flame speed of mixtures comprising R-152a, withincreasing fluorine ratio resulting in lower flame speeds. The data inthis reference teach that the fluorine ratio needs to be greater thanabout 0.65 for the flame speed to drop to zero, in other words, for themixture to be non-flammable.

Similarly, Minor et al (Du Pont Patent Application WO2007/053697)provide teaching on the flammability of many hydrofluoroolefins, showingthat such compounds could be expected to be non-flammable if thefluorine ratio is greater than about 0.7.

In view of this prior art teaching, it is unexpected that that mixturesof R-1234ze(E) with flammable fluorocarbons such as R-1234yf or R-1243zfwill remain non-flammable in air at 23° C. if the fluorine ratio R_(f)of the mixture is greater than about 0.57.

Furthermore, we identified that if the fluorine ratio is greater thanabout 0.46 then the composition can be expected to have a lowerflammable limit in air of greater than 6% v/v at room temperature.

By producing low- or non-flammable R-744/third component/R-1234ze(E)blends containing unexpectedly low amounts of R-1234ze(E), the amountsof the third component, in particular, in such compositions areincreased. This is believed to result in heat transfer compositionsexhibiting increased cooling capacity and/or decreased pressure drop,compared to equivalent compositions containing higher amounts of (e.g.almost 100%) R-1234ze(E).

Thus, the compositions of the invention exhibit a completely unexpectedcombination of low-/non-flammability, low GWP and improved refrigerationperformance properties. Some of these refrigeration performanceproperties are explained in more detail below.

Temperature glide, which can be thought of as the difference betweenbubble point and dew point temperatures of a zeotropic (non-azeotropic)mixture at constant pressure, is a characteristic of a refrigerant; ifit is desired to replace a fluid with a mixture then it is oftenpreferable to have similar or reduced glide in the alternative fluid. Inan embodiment, the compositions of the invention are zeotropic.

Advantageously, the volumetric refrigeration capacity of thecompositions of the invention is at least 85% of the existingrefrigerant fluid it is replacing, preferably at least 90% or even atleast 95%.

The compositions of the invention typically have a volumetricrefrigeration capacity that is at least 90% of that of R-1234yf.Preferably, the compositions of the invention have a volumetricrefrigeration capacity that is at least 95% of that of R-1234yf, forexample from about 95% to about 120% of that of R-1234yf.

In one embodiment, the cycle efficiency (Coefficient of Performance,COP) of the compositions of the invention is within about 5% or evenbetter than the existing refrigerant fluid it is replacing

Conveniently, the compressor discharge temperature of the compositionsof the invention is within about 15K of the existing refrigerant fluidit is replacing, preferably about 10K or even about 5K.

The compositions of the invention preferably have energy efficiency atleast 95% (preferably at least 98%) of R-134a under equivalentconditions, while having reduced or equivalent pressure dropcharacteristics and cooling capacity at 95% or higher of R-134a values.Advantageously the compositions have higher energy efficiency and lowerpressure drop characteristics than R-134a under equivalent conditions.The compositions also advantageously have better energy efficiency andpressure drop characteristics than R-1234yf alone.

The heat transfer compositions of the invention are suitable for use inexisting designs of equipment, and are compatible with all classes oflubricant currently used with established HFC refrigerants. They may beoptionally stabilized or compatibilized with mineral oils by the use ofappropriate additives.

Preferably, when used in heat transfer equipment, the composition of theinvention is combined with a lubricant.

Conveniently, the lubricant is selected from the group consisting ofmineral oil, silicone oil, polyalkyl benzenes (PABs), polyol esters(POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAGesters), polyvinyl ethers (PVEs), poly (alpha-olefins) and combinationsthereof.

Advantageously, the lubricant further comprises a stabiliser.

Preferably, the stabiliser is selected from the group consisting ofdiene-based compounds, phosphates, phenol compounds and epoxides, andmixtures thereof.

Conveniently, the composition of the invention may be combined with aflame retardant.

Advantageously, the flame retardant is selected from the groupconsisting of tri-(2-chloroethyl)-phosphate, (chloropropyl) phosphate,tri-(2,3-dibromopropyl)-phosphate, tri-(1,3-dichloropropyl)-phosphate,diammonium phosphate, various halogenated aromatic compounds, antimonyoxide, aluminium trihydrate, polyvinyl chloride, a fluorinatediodocarbon, a fluorinated bromocarbon, trifluoro iodomethane,perfluoroalkyl amines, bromo-fluoroalkyl amines and mixtures thereof.

Preferably, the heat transfer composition is a refrigerant composition.

In one embodiment, the invention provides a heat transfer devicecomprising a composition of the invention.

Preferably, the heat transfer device is a refrigeration device.

Conveniently, the heat transfer device is selected from the groupconsisting of automotive air conditioning systems, residential airconditioning systems, commercial air conditioning systems, residentialrefrigerator systems, residential freezer systems, commercialrefrigerator systems, commercial freezer systems, chiller airconditioning systems, chiller refrigeration systems, and commercial orresidential heat pump systems. Preferably, the heat transfer device is arefrigeration device or an air-conditioning system.

The compositions of the invention are particularly suitable for use inmobile air-conditioning applications, such as automotiveair-conditioning systems (e.g. heat pump cycle for automotiveair-conditioning).

Advantageously, the heat transfer device contains a centrifugal-typecompressor.

The invention also provides the use of a composition of the invention ina heat transfer device as herein described.

According to a further aspect of the invention, there is provided ablowing agent comprising a composition of the invention.

According to another aspect of the invention, there is provided afoamable composition comprising one or more components capable offorming foam and a composition of the invention.

Preferably, the one or more components capable of forming foam areselected from polyurethanes, thermoplastic polymers and resins, such aspolystyrene, and epoxy resins.

According to a further aspect of the invention, there is provided a foamobtainable from the foamable composition of the invention.

Preferably the foam comprises a composition of the invention.

According to another aspect of the invention, there is provided asprayable composition comprising a material to be sprayed and apropellant comprising a composition of the invention.

According to a further aspect of the invention, there is provided amethod for cooling an article which comprises condensing a compositionof the invention and thereafter evaporating said composition in thevicinity of the article to be cooled.

According to another aspect of the invention, there is provided a methodfor heating an article which comprises condensing a composition of theinvention in the vicinity of the article to be heated and thereafterevaporating said composition.

According to a further aspect of the invention, there is provided amethod for extracting a substance from biomass comprising contacting thebiomass with a solvent comprising a composition of the invention, andseparating the substance from the solvent.

According to another aspect of the invention, there is provided a methodof cleaning an article comprising contacting the article with a solventcomprising a composition of the invention.

According to a further aspect of the invention, there is provided amethod for extracting a material from an aqueous solution comprisingcontacting the aqueous solution with a solvent comprising a compositionof the invention, and separating the material from the solvent.

According to another aspect of the invention, there is provided a methodfor extracting a material from a particulate solid matrix comprisingcontacting the particulate solid matrix with a solvent comprising acomposition of the invention, and separating the material from thesolvent.

According to a further aspect of the invention, there is provided amechanical power generation device containing a composition of theinvention.

Preferably, the mechanical power generation device is adapted to use aRankine Cycle or modification thereof to generate work from heat.

According to another aspect of the invention, there is provided a methodof retrofitting a heat transfer device comprising the step of removingan existing heat transfer fluid, and introducing a composition of theinvention. Preferably, the heat transfer device is a refrigerationdevice or (a static) air conditioning system. Advantageously, the methodfurther comprises the step of obtaining an allocation of greenhouse gas(e.g. carbon dioxide) emission credit.

In accordance with the retrofitting method described above, an existingheat transfer fluid can be fully removed from the heat transfer devicebefore introducing a composition of the invention. An existing heattransfer fluid can also be partially removed from a heat transferdevice, followed by introducing a composition of the invention.

In another embodiment wherein the existing heat transfer fluid isR-134a, and the composition of the invention contains R134a,R-1234ze(E), R-744, the third component and any R-125 present (andoptional components such as a lubricant, a stabiliser or an additionalflame retardant), R-1234ze(E) and R-744, etc, can be added to the R-134ain the heat transfer device, thereby forming the compositions of theinvention, and the heat transfer device of the invention, in situ. Someof the existing R-134a may be removed from the heat transfer deviceprior to adding the R-1234ze(E), R-744, etc, to facilitate providing thecomponents of the compositions of the invention in the desiredproportions.

Thus, the invention provides a method for preparing a composition and/orheat transfer device of the invention comprising introducingR-1234ze(E), R-744, the third component, any R-125 desired, and optionalcomponents such as a lubricant, a stabiliser or an additional flameretardant, into a heat transfer device containing an existing heattransfer fluid which is R-134a. Optionally, at least some of the R-134ais removed from the heat transfer device before introducing theR-1234ze(E), R-744, etc.

Of course, the compositions of the invention may also be prepared simplyby mixing the R-1234ze(E), R-744, the third component, any R-125 desired(and optional components such as a lubricant, a stabiliser or anadditional flame retardant) in the desired proportions. The compositionscan then be added to a heat transfer device (or used in any other way asdefined herein) that does not contain R-134a or any other existing heattransfer fluid, such as a device from which R-134a or any other existingheat transfer fluid have been removed.

In a further aspect of the invention, there is provided a method forreducing the environmental impact arising from operation of a productcomprising an existing compound or composition, the method comprisingreplacing at least partially the existing compound or composition with acomposition of the invention. Preferably, this method comprises the stepof obtaining an allocation of greenhouse gas emission credit.

By environmental impact we include the generation and emission ofgreenhouse warming gases through operation of the product.

As mentioned above, this environmental impact can be considered asincluding not only those emissions of compounds or compositions having asignificant environmental impact from leakage or other losses, but alsoincluding the emission of carbon dioxide arising from the energyconsumed by the device over its working life. Such environmental impactmay be quantified by the measure known as Total Equivalent WarmingImpact (TEWI). This measure has been used in quantification of theenvironmental impact of certain stationary refrigeration and airconditioning equipment, including for example supermarket refrigerationsystems (see, for example,http://en.wikipedia.org/wiki/Total_equivalent_warming_impact).

The environmental impact may further be considered as including theemissions of greenhouse gases arising from the synthesis and manufactureof the compounds or compositions. In this case the manufacturingemissions are added to the energy consumption and direct loss effects toyield the measure known as Life-Cycle Carbon Production (LCCP, see forexample http://www.sae.org/events/aars/presentations/2007papasavva.pdf).The use of LCCP is common in assessing environmental impact ofautomotive air conditioning systems.

Emission credit(s) are awarded for reducing pollutant emissions thatcontribute to global warming and may, for example, be banked, traded orsold. They are conventionally expressed in the equivalent amount ofcarbon dioxide. Thus if the emission of 1 kg of R-134a is avoided thenan emission credit of 1×1300=1300 kg CO₂ equivalent may be awarded.

In another embodiment of the invention, there is provided a method forgenerating greenhouse gas emission credit(s) comprising (i) replacing anexisting compound or composition with a composition of the invention,wherein the composition of the invention has a lower GWP than theexisting compound or composition; and (ii) obtaining greenhouse gasemission credit for said replacing step.

In a preferred embodiment, the use of the composition of the inventionresults in the equipment having a lower Total Equivalent Warming Impact,and/or a lower Life-Cycle Carbon Production than that which would beattained by use of the existing compound or composition.

These methods may be carried out on any suitable product, for example inthe fields of air-conditioning, refrigeration (e.g. low and mediumtemperature refrigeration), heat transfer, blowing agents, aerosols orsprayable propellants, gaseous dielectrics, cryosurgery, veterinaryprocedures, dental procedures, fire extinguishing, flame suppression,solvents (e.g. carriers for flavorings and fragrances), cleaners, airhorns, pellet guns, topical anesthetics, and expansion applications.Preferably, the field is air-conditioning or refrigeration.

Examples of suitable products include heat transfer devices, blowingagents, foamable compositions, sprayable compositions, solvents andmechanical power generation devices. In a preferred embodiment, theproduct is a heat transfer device, such as a refrigeration device or anair-conditioning unit.

The existing compound or composition has an environmental impact asmeasured by GWP and/or TEWI and/or LCCP that is higher than thecomposition of the invention which replaces it. The existing compound orcomposition may comprise a fluorocarbon compound, such as a perfluoro-,hydrofluoro-, chlorofluoro- or hydrochlorofluoro-carbon compound or itmay comprise a fluorinated olefin

Preferably, the existing compound or composition is a heat transfercompound or composition such as a refrigerant. Examples of refrigerantsthat may be replaced include R-134a, R-152a, R-1234yf, R-410A, R-407A,R-407B, R-407C, R507, R-22 and R-404A. The compositions of the inventionare particularly suited as replacements for R-134a, R-152a or R-1234yf,especially R-134a or R-1234yf.

Any amount of the existing compound or composition may be replaced so asto reduce the environmental impact. This may depend on the environmentalimpact of the existing compound or composition being replaced and theenvironmental impact of the replacement composition of the invention.Preferably, the existing compound or composition in the product is fullyreplaced by the composition of the invention.

The invention is illustrated by the following non-limiting examples.

EXAMPLES Flammability

It was found by experimentation using the ASHRAE Std 34 test method thatthe flammability of mixtures of R1243zf in R-1234ze(E) was significantlyreduced compared to flammability of pure R-1243zf or R-1234yf.

In particular it was found that mixtures of R-1243zf in R-1234ze(E) werenon-flammable at 23° C. in air of 50% relative humidity if the molarratio of R-1243zf:R-1234ze(E) was less than about 14:86, correspondingto a mass ratio of 12:88.

Furthermore, the lower flammable limit of mixtures containing higheramounts of R-1243zf was found to be greater than 6% v/v if the molarratio of R1243zf:R1234ze(E) was less than about 1. The lower flammablelimit of R-1234yf was determined to be ˜6% in the same test apparatusand thus binary mixtures of R-1243zf:R1234ze(E) having a molar ratiozf:ze of less than about 1:1 exhibited an improved value of lowerflammable limit compared to pure R-1234yf.

Modelled Performance Data

Generation of Accurate Physical Property Model

The physical properties of R-1234yf and R-1234ze(E) required to modelrefrigeration cycle performance, namely critical point, vapour pressure,liquid and vapour enthalpy, liquid and vapour density and heatcapacities of vapour and liquid were accurately determined byexperimental methods over the pressure range 0-200 bar and temperaturerange −40 to 200° C., and the resulting data used to generate Helmholtzfree energy equation of state models of the Span-Wagner type for thefluid in the NIST REFPROP Version 8.0 software, which is more fullydescribed in the user guide www.nist.gov/srd/PDFfiles/REFPROP8.PDF, andis incorporated herein by reference. The variation of ideal gas enthalpyof both fluids with temperature was estimated using molecular modellingsoftware Hyperchem v7.5 (which is incorporated herein by reference) andthe resulting ideal gas enthalpy function was used in the regression ofthe equation of state for these fluids. The predictions of this modelfor R1234yf and R1234ze(E) were compared to the predictions yielded byuse of the standard files for R1234yf and R1234ze(E) included in REFPROPVersion 9.0 (incorporated herein by reference). It was found that closeagreement was obtained for each fluid's properties.

The vapour liquid equilibrium behaviour of R-1234ze(E) was studied in aseries of binary pairs with carbon dioxide, R-32, R-125, R-134a, R-152a,R-161, propane and propylene over the temperature range −40 to +60° C.,which encompasses the practical operating range of most refrigerationand air conditioning systems. The composition was varied over the fullcompositional space for each binary in the experimental programme,Mixture parameters for each binary pair were regressed to theexperimentally obtained data and the parameters were also incorporatedinto the REFPROP software model. The academic literature was nextsearched for data on the vapour liquid equilibrium behaviour of carbondioxide with the hydrofluorocarbons R-32, R-125, R-152a, R-161 andR-152a. The VLE data obtained from sources referenced in the articleApplications of the simple multi-fluid model to correlations of thevapour-liquid equilibrium of refrigerant mixtures containing carbondioxide, by R. Akasaka, Journal of Thermal Science and Technology,159-168, 4, 1, 2009 (which is incorporated herein by reference) werethen used to generate mixing parameters for the relevant binary mixturesand these were then also incorporated into the REFPROP model. Thestandard REFPROP mixing parameters for carbon dioxide with propane andpropylene were also incorporated to this model.

The resulting software model was used to compare the performance ofselected fluids of the invention with R-134a in a heat pumping cycleapplication.

Heat Pumping Cycle Comparison

In a first comparison the behaviour of the fluids was assessed for asimple vapour compression cycle with conditions typical of automotiveheat pumping duty in low winter ambient temperatures. In this comparisonpressure drop effects were included in the model by assignation of arepresentative expected pressure drop to the reference fluid (R-134a)followed by estimation of the equivalent pressure drop for the mixedrefrigerant of the invention in the same equipment at the same heatingcapacity. The comparison was made on the basis of equal heat exchangerarea for the reference fluid (R-134a) and for the mixed fluids of theinvention. The methodology used for this model was derived using theassumptions of equal effective overall heat transfer coefficient forrefrigerant condensation, refrigerant evaporation, refrigerant liquidsubcooling and refrigerant vapour superheating processes to derive aso-called UA model for the process. The derivation of such a model fornonazeotropic refrigerant mixtures in heat pump cycles is more fullyexplained in the reference text Vapor Compression Heat Pumps withrefrigerant mixtures by R Radermacher & Y Hwang (pub Taylor & Francis2005) Chapter 3, which is incorporated herein by reference.

Briefly, the model starts with an initial estimate of the condensing andevaporating pressures for the refrigerant mixture and estimates thecorresponding temperatures at the beginning and end of the condensationprocess in the condenser and the evaporation process in the evaporator.These temperatures are then used in conjunction with the specifiedchanges in air temperatures over condenser and evaporator to estimate arequired overall heat exchanger area for each of the condenser andevaporator. This is an iterative calculation: the condensing andevaporating pressures are adjusted to ensure that the overall heatexchanger areas are the same for reference fluid and for the mixedrefrigerant.

For the comparison the worst case for heat pumping in automotiveapplication was assumed with the following assumptions for airtemperature and for R-134a cycle conditions.

Cycle Conditions

Ambient air temperature on to condenser and evaporator −15° C. Airtemperature leaving evaporator: −25° C. Air temperature leavingcondenser (passenger air) +45° C. R134a evaporating temperature −30° C.R-134a condensing temperature +50° C. Subcooling of refrigerant incondenser 1 K Superheating of refrigerant in evaporator 5 K Compressorsuction temperature 0° C. Compressor isentropic efficiency 66% Passengerair heating load 2 kW Pressure drop in evaporator for R-134a 0.03 barPressure drop in condenser for R-134a 0.03 bar Pressure drop in suctionline for R-134a 0.03 bar

The model assumed countercurrent flow for each heat exchanger in itscalculation of effective temperature differences for each of the heattransfer processes.

Condensing and evaporating temperatures for compositions was adjusted togive equivalent usage of heat exchange area as reference fluid. Thefollowing input parameters were used.

Parameter Reference Refrigerant R134a Mean condenser temperature ° C. 50Mean evaporator temperature ° C. −30 Condenser subcooling K 1 Evaporatorsuperheat K 5 Suction diameter mm 16.2 Heating capacity kW 2 Evaporatorpressure drop bar 0.03 Suction line pressure drop bar 0.03 Condenserpressure drop bar 0.03 Compressor suction temperature ° C. 0 Isentropicefficiency   66% Evaporator air on ° C. −15.00 Evaporator air off ° C.−25.00 Condenser air on ° C. −15.00 Condenser air off ° C. 45.00Condenser area 100.0% 100.0% Evaporator area 100.0% 100.0%

Using the above model, the performance data for the reference R-134a isshown below.

COP (heating) 2.11 COP (heating) relative to Reference 100.0% Volumetricheating capacity at suction kJ/m³ 879 Capacity relative to Reference100.0% Critical temperature ° C. 101.06 Critical pressure bar 40.59Condenser enthalpy change kJ/kg 237.1 Pressure ratio 16.36 Refrigerantmass flow kg/hr 30.4 Compressor discharge temperature ° C. 125.5Evaporator inlet pressure bar 0.86 Condenser inlet pressure bar 13.2Evaporator inlet temperature ° C. −29.7 Evaporator dewpoint ° C. −30.3Evaporator exit gas temperature ° C. −25.3 Evaporator mean temperature °C. −30.0 Evaporator glide (out-in) K −0.6 Compressor suction pressurebar 0.81 Compressor discharge pressure bar 13.2 Suction line pressuredrop Pa/m 292 Pressure drop relative to reference 100.0% Condenser dewpoint ° C. 50.0 Condenser bubble point ° C. 50.0 Condenser exit liquidtemperature ° C. 49.0 Condenser mean temperature ° C. 50.0 Condenserglide (in-out) K 0.1

The generated performance data for selected compositions of theinvention is set out in the following Tables. The tables show keyparameters of the heat pump cycle, including operating pressures,volumetric heating capacity, energy efficiency (expressed as coefficientof performance for heating COP) compressor discharge temperature andpressure drops in pipework. The volumetric heating capacity of arefrigerant is a measure of the amount of heating which can be obtainedfor a given size of compressor operating at fixed speed. The coefficientof performance (COP) is the ratio of the amount of heat energy deliveredin the condenser of the heat pump cycle to the amount of work consumedby the compressor.

The performance of R-134a is taken as the reference point for comparisonof heating capacity, energy efficiency and pressure drop. This fluid isused as a reference for comparison of the ability of the fluids of theinvention to be used in the heat pump mode of an automotive combined airconditioning and heat pump system.

It should be noted in passing that the utility of fluids of theinvention is not limited to automotive systems. Indeed these fluids canbe used in so-called stationary (residential or commercial) equipment.Currently the main fluids used in such stationary equipment are R-410A(having a GWP of 2100) or R22 (having a GWP of 1800 and an ozonedepletion potential of 0.05). The use of the fluids of the invention insuch stationary equipment offers the ability to realise similar utilitybut with fluids having no ozone depletion potential and significantlyreduced GWP compared to R410A.

It is evident that fluids of the invention can provide improved energyefficiency compared to R-134a or R-410A. It is unexpectedly found thatthe addition of carbon dioxide to the refrigerants of the invention canincrease the COP of the resulting cycle above that of R-134a, even incase where admixture of the other mixture components would result in afluid having worse energy efficiency than R-134a.

It is further found for all the fluids of the invention thatcompositions up to about 30% w/w of CO₂ can be used which yieldrefrigerant fluids whose critical temperature is about 70° C. or higher.This is particularly significant for stationary heat pumpingapplications where R-410A is currently used. The fundamentalthermodynamic efficiency of a vapour compression process is affected byproximity of the critical temperature to the condensing temperature.R-410A has gained acceptance and can be considered an acceptable fluidfor this application; its critical temperature is 71° C. It hasunexpectedly been found that significant quantities of CO₂ (criticaltemperature 31° C.) can be incorporated in fluids of the invention toyield mixtures having similar or higher critical temperature to R-410A.Preferred compositions of the invention therefore have criticaltemperatures are about 70° C. or higher.

The heating capacity of the preferred fluids of the invention typicallyexceeds that of R134a. It is thought that R-134a alone, operated in anautomotive a/c and heat pump system, cannot provide all of the potentialpassenger air heating demand in heat pump mode. Therefore higher heatingcapacities than R-134a are preferred for potential use in an automotivea/c and heat pump application. The fluids of the invention offer theability to optimise fluid capacity and energy efficiency for both airconditioning and cooling modes so as to provide an improved overallenergy efficiency for both duties.

For reference, the heating capacity of R-410A in the same cycleconditions was estimated at about 290% of the R-134a value and thecorresponding energy efficiency was found to be about 106% of the R-134areference value.

It is evident by inspection of the tables that fluids of the inventionhave been discovered having comparable heating capacities and energyefficiencies to R-410A, allowing adaption of existing R-410A technologyto use the fluids of the invention if so desired.

Some further benefits of the fluids of the invention are described inmore detail below.

At equivalent cooling capacity the compositions of the invention offerreduced pressure drop compared to R-134a. This reduced pressure dropcharacteristic is believed to result in further improvement in energyefficiency (through reduction of pressure losses) in a real system.Pressure drop effects are of particular significance for automotive airconditioning and heat pump applications so these fluids offer particularadvantage for this application.

The performance of fluids of the invention were compared to binarymixtures of CO₂/R1234ze(E). For all the ternary compositions of theinvention apart from CO₂/R1234yf/R1234ze(E) the energy efficiency of theternary mixtures was increased relative to the binary mixture havingequivalent CO₂ content. These mixtures therefore represent an improvedsolution relative to the CO₂/R1234ze(E) binary refrigerant mixture, atleast for CO₂ content less than 30% w/w.

It was possible to generate CO₂/R1234yf/R1234ze(E) mixtures havingcomparable or slightly higher energy efficiency to R-134a. Thusunexpectedly this ternary fluid system of the invention provides a meansto ameliorate the poor intrinsic energy efficiency of R-1234yf.

The performance of selected R-744/R-1243zf/R-1234ze(E) ternarycompositions of the invention was also modelled using the heat pumpcycle previously discussed. The results are tabulated in the appendedtables. It was found that the addition of R1243zf to R1234ze(E) improvedthe specific pressure drop and volumetric capacity of the mixture forany given amount of admixed R-744. It was also found that the criticaltemperature of the ternary mixture would be increased as compared to abinary R-744/R-1234ze(E) mixture having equivalent volumetric capacity.The increased critical temperature is important for improvingperformance in for example a dual mode (air conditioning/heat pump)system operating as an air conditioner in a hot ambient climate.

The energy efficiency (COP) of the mixtures exhibited maximacorresponding to optimal R-744 content for a given level of R-1243zf inthe mixture. It was also observed that the maximum value of COP thusattained increased as the level of R-1243zf increased.

TABLE 1 Theoretical Performance Data of SelectedR-744/R-1234yf/R-1234ze(E) blends containing 0-14% R-744 and 5% R-1234yfComposition CO₂/R-1234yf/R-1234ze(E) % by weight 

0/5/95 2/5/93 4/5/91 6/5/89 8/5/87 10/5/85 12/5/83 14/5/81 COP (heating)1.99 2.05 2.10 2.13 2.16 2.18 2.19 2.20 COP (heating) relative toReference 94.2% 97.2% 99.4% 101.0% 102.3% 103.2% 103.9% 104.5%Volumetric heating capacity at suction kJ/m³ 638 721 807 896 987 10821180 1280 Capacity relative to Reference 72.6% 82.1% 91.8% 101.9% 112.4%123.2% 134.3% 145.7% Critical temperature ° C. 109.13 105.19 101.4998.00 94.71 91.59 88.65 85.86 Critical pressure bar 36.92 37.75 38.5839.40 40.22 41.03 41.84 42.64 Condenser enthalpy change kJ/kg 208.0221.4 232.7 242.2 250.4 257.6 264.1 269.9 Pressure ratio 18.41 18.6718.74 18.64 18.40 18.08 17.70 17.28 Refrigerant mass flow kg/hr 34.632.5 30.9 29.7 28.8 27.9 27.3 26.7 Compressor discharge temperature ° C.112.1 116.4 120.4 124.0 127.2 130.2 133.0 135.6 Evaporator inletpressure bar 0.68 0.72 0.78 0.84 0.91 0.99 1.07 1.16 Condenser inletpressure bar 11.0 12.2 13.5 14.7 15.9 17.1 18.3 19.5 Evaporator inlettemperature ° C. −29.0 −29.7 −30.4 −31.2 −32.0 −32.8 −33.7 −34.7Evaporator dewpoint ° C. −30.0 −29.5 −28.8 −28.0 −27.2 −26.4 −25.7 −24.9Evaporator exit gas temperature ° C. −25.0 −24.5 −23.8 −23.0 −22.2 −21.4−20.7 −19.9 Evaporator mean temperature ° C. −29.5 −29.6 −29.6 −29.6−29.6 −29.6 −29.7 −29.8 Evaporator glide (out-in) K −1.0 0.2 1.6 3.1 4.76.4 8.1 9.7 Compressor suction pressure bar 0.60 0.66 0.72 0.79 0.870.95 1.03 1.13 Compressor discharge pressure bar 11.0 12.2 13.5 14.715.9 17.1 18.3 19.5 Suction line pressure drop Pa/m 449 379 327 285 252226 203 184 Pressure drop relative to reference 153.8%  129.8%  111.8% 97.7%  86.5%  77.2%  69.5%  63.0% Condenser dew point ° C. 53.3 55.356.9 58.2 59.2 60.0 60.5 60.8 Condenser bubble point ° C. 52.8 46.9 42.438.8 36.0 33.7 31.9 30.4 Condenser exit liquid temperature ° C. 51.845.9 41.4 37.8 35.0 32.7 30.9 29.4 Condenser mean temperature ° C. 53.151.1 49.6 48.5 47.6 46.9 46.2 45.6 Condenser glide (in-out) K 0.6 8.314.5 19.4 23.3 26.3 28.6 30.4

TABLE 2 Theoretical Performance Data of SelectedR-744/R-1234yf/R-1234ze(E) blends containing 16-30% R-744 and 5%R-1234yf Composition CO₂/R-1234yf/R-1234ze(E) % by weight 

16/5/79 18/5/77 20/5/75 22/5/73 24/5/71 26/5/69 28/5/67 30/5/65 COP(heating) 2.21 2.22 2.23 2.23 2.23 2.23 2.23 2.23 COP (heating) relativeto Reference 105.0% 105.3% 105.6% 105.7% 105.8% 105.8% 105.8% 105.7%Volumetric heating capacity at suction kJ/m³ 1383 1488 1594 1702 18101920 2030 2141 Capacity relative to Reference 157.4% 169.3% 181.4%193.7% 206.0% 218.5% 231.0% 243.6% Critical temperature ° C. 83.21 80.6978.29 76.01 73.83 71.75 69.76 67.85 Critical pressure bar 43.44 44.2445.04 45.83 46.62 47.41 48.19 48.97 Condenser enthalpy change kJ/kg275.3 280.3 285.1 289.6 294.0 298.2 302.3 306.4 Pressure ratio 16.8516.42 16.00 15.59 15.20 14.82 14.47 14.14 Refrigerant mass flow kg/hr26.2 25.7 25.3 24.9 24.5 24.1 23.8 23.5 Compressor discharge temperature° C. 138.1 140.5 142.8 145.0 147.3 149.5 151.6 153.8 Evaporator inletpressure bar 1.25 1.35 1.45 1.56 1.67 1.78 1.89 2.01 Condenser inletpressure bar 20.6 21.7 22.8 23.9 25.0 26.1 27.1 28.2 Evaporator inlettemperature ° C. −35.6 −36.7 −37.7 −38.8 −39.8 −40.9 −41.9 −42.9Evaporator dewpoint ° C. −24.2 −23.5 −22.9 −22.4 −21.9 −21.5 −21.2 −20.9Evaporator exit gas temperature ° C. −19.2 −18.5 −17.9 −17.4 −16.9 −16.5−16.2 −15.9 Evaporator mean temperature ° C. −29.9 −30.1 −30.3 −30.6−30.9 −31.2 −31.5 −31.9 Evaporator glide (out-in) K 11.4 13.1 14.8 16.417.9 19.4 20.8 22.0 Compressor suction pressure bar 1.22 1.32 1.43 1.531.65 1.76 1.87 1.99 Compressor discharge pressure bar 20.6 21.7 22.823.9 25.0 26.1 27.1 28.2 Suction line pressure drop Pa/m 168 154 142 131122 114 107 100 Pressure drop relative to reference  57.5%  52.7%  48.6% 45.0%  41.8%  39.0%  36.5%  34.3% Condenser dew point ° C. 61.0 61.060.9 60.7 60.4 60.0 59.5 58.9 Condenser bubble point ° C. 29.2 28.1 27.326.5 25.9 25.3 24.9 24.4 Condenser exit liquid temperature ° C. 28.227.1 26.3 25.5 24.9 24.3 23.9 23.4 Condenser mean temperature ° C. 45.144.6 44.1 43.6 43.1 42.6 42.2 41.7 Condenser glide (in-out) K 31.8 32.933.7 34.2 34.5 34.6 34.6 34.5

TABLE 3 Theoretical Performance Data of SelectedR-744/R-1234yf/R-1234ze(E) blends containing 0-14% R-744 and 10%R-1234yf Composition CO₂/R-1234yf/R-1234ze(E) % by weight 

0/10/90 2/10/88 4/10/86 6/10/84 8/10/82 10/10/80 12/10/78 14/10/76 COP(heating) 1.98 2.05 2.09 2.12 2.15 2.17 2.18 2.20 COP (heating) relativeto Reference 94.0% 97.0% 99.2% 100.8% 102.0% 102.9% 103.6% 104.1%Volumetric heating capacity at suction kJ/m³ 661 747 835 927 1022 11191219 1322 Capacity relative to Reference 75.2% 85.0% 95.1% 105.5% 116.3%127.3% 138.7% 150.5% Critical temperature ° C. 108.37 104.45 100.7797.30 94.03 90.94 88.01 85.24 Critical pressure bar 37.22 38.12 39.0039.88 40.75 41.62 42.47 43.32 Condenser enthalpy change kJ/kg 205.7219.1 230.2 239.7 247.7 254.8 261.0 266.7 Pressure ratio 18.07 18.3518.42 18.33 18.09 17.78 17.40 16.99 Refrigerant mass flow kg/hr 35.032.9 31.3 30.0 29.1 28.3 27.6 27.0 Compressor discharge temperature ° C.111.4 115.7 119.7 123.3 126.5 129.4 132.2 134.8 Evaporator inletpressure bar 0.70 0.75 0.81 0.87 0.95 1.03 1.11 1.21 Condenser inletpressure bar 11.3 12.6 13.9 15.1 16.4 17.6 18.8 20.0 Evaporator inlettemperature ° C. −29.1 −29.8 −30.5 −31.3 −32.1 −32.9 −33.8 −34.8Evaporator dewpoint ° C. −29.8 −29.3 −28.6 −27.9 −27.1 −26.3 −25.5 −24.8Evaporator exit gas temperature ° C. −24.8 −24.3 −23.6 −22.9 −22.1 −21.3−20.5 −19.8 Evaporator mean temperature ° C. −29.4 −29.5 −29.6 −29.6−29.6 −29.6 −29.7 −29.8 Evaporator glide (out-in) K −0.7 0.5 1.9 3.4 5.06.6 8.3 10.0 Compressor suction pressure bar 0.63 0.69 0.75 0.83 0.900.99 1.08 1.18 Compressor discharge pressure bar 11.3 12.6 13.9 15.116.4 17.6 18.8 20.0 Suction line pressure drop Pa/m 437 369 318 278 246220 198 180 Pressure drop relative to reference 149.7%  126.3%  108.8%  95.2%  84.2%  75.3%  67.9%  61.6% Condenser dew point ° C. 53.5 55.457.0 58.3 59.3 60.0 60.5 60.7 Condenser bubble point ° C. 52.6 46.8 42.238.7 35.9 33.7 31.9 30.4 Condenser exit liquid temperature ° C. 51.645.8 41.2 37.7 34.9 32.7 30.9 29.4 Condenser mean temperature ° C. 53.151.1 49.6 48.5 47.6 46.8 46.2 45.6 Condenser glide (in-out) K 0.9 8.614.8 19.6 23.4 26.3 28.6 30.3

TABLE 4 Theoretical Performance Data of SelectedR-744/R-1234yf/R-1234ze(E) blends containing 16-30% R-744 and 10%R-1234yf Composition CO₂/R-1234yf/R-1234ze(E) % by weight 

16/10/74 18/10/72 20/10/70 22/10/68 24/10/66 26/10/64 28/10/62 30/10/60COP (heating) 2.20 2.21 2.22 2.22 2.22 2.22 2.22 2.22 COP (heating)relative 104.6% 104.9% 105.1% 105.3% 105.3% 105.3% 105.3% 105.2% toReference Volumetric heating capacity kJ/m³ 1427 1535 1644 1754 18661979 2093 2207 at suction Capacity relative to Reference 162.4% 174.7%187.1% 199.7% 212.4% 225.2% 238.2% 251.2% Critical temperature ° C.82.60 80.10 77.71 75.44 73.28 71.21 69.23 67.34 Critical pressure bar44.17 45.00 45.84 46.66 47.49 48.30 49.12 49.93 Condenser enthalpychange kJ/kg 271.9 276.8 281.4 285.7 289.9 293.9 297.9 301.7 Pressureratio 16.56 16.13 15.71 15.30 14.91 14.53 14.18 13.84 Refrigerant massflow kg/hr 26.5 26.0 25.6 25.2 24.8 24.5 24.2 23.9 Compressor dischargetemperature ° C. 137.2 139.5 141.8 144.0 146.2 148.3 150.4 152.5Evaporator inlet pressure bar 1.30 1.41 1.51 1.62 1.74 1.86 1.98 2.10Condenser inlet pressure bar 21.1 22.3 23.4 24.5 25.6 26.7 27.8 28.8Evaporator inlet temperature ° C. −35.7 −36.7 −37.8 −38.8 −39.9 −40.9−41.9 −42.9 Evaporator dewpoint ° C. −24.1 −23.4 −22.9 −22.3 −21.9 −21.5−21.1 −20.9 Evaporator exit gas temperature ° C. −19.1 −18.4 −17.9 −17.3−16.9 −16.5 −16.1 −15.9 Evaporator mean temperature ° C. −29.9 −30.1−30.3 −30.6 −30.9 −31.2 −31.5 −31.9 Evaporator glide (out-in) K 11.713.3 14.9 16.5 18.0 19.4 20.8 22.0 Compressor suction pressure bar 1.281.38 1.49 1.60 1.72 1.84 1.96 2.08 Compressor discharge pressure bar21.1 22.3 23.4 24.5 25.6 26.7 27.8 28.8 Suction line pressure drop Pa/m164 151 139 129 120 112 105 98 Pressure drop relative to reference 56.2%  51.6%  47.6%  44.1%  41.0%  38.2%  35.8%  33.6% Condenser dewpoint ° C. 60.8 60.8 60.6 60.3 60.0 59.5 59.0 58.4 Condenser bubblepoint ° C. 29.2 28.2 27.4 26.7 26.1 25.6 25.1 24.8 Condenser exit liquidtemperature ° C. 28.2 27.2 26.4 25.7 25.1 24.6 24.1 23.8 Condenser meantemperature ° C. 45.0 44.5 44.0 43.5 43.0 42.6 42.1 41.6 Condenser glide(in-out) K 31.6 32.6 33.2 33.7 33.9 33.9 33.8 33.6

TABLE 5 Theoretical Performance Data of SelectedR-744/R-1234yf/R-1234ze(E) blends containing 0-14% R-744 and 20%R-1234yf Composition CO₂/R-1234yf/R-1234ze(E) % by weight 

0/20/80 2/20/78 4/20/76 6/20/74 8/20/72 10/20/70 12/20/68 14/20/66 COP(heating) 1.97 2.03 2.08 2.11 2.14 2.16 2.17 2.18 COP (heating) relativeto Reference 93.4% 96.5% 98.7% 100.2% 101.4% 102.2% 102.9% 103.4%Volumetric heating capacity at suction kJ/m³ 706 798 892 989 1089 11921297 1405 Capacity relative to Reference 80.3% 90.8% 101.5% 112.5%123.9% 135.6% 147.6% 159.9% Critical temperature ° C. 106.85 102.9899.34 95.92 92.68 89.63 86.74 83.99 Critical pressure bar 37.65 38.6939.70 40.70 41.68 42.65 43.61 44.55 Condenser enthalpy change kJ/kg201.1 214.5 225.5 234.7 242.5 249.2 255.2 260.5 Pressure ratio 17.4217.73 17.83 17.75 17.53 17.22 16.85 16.44 Refrigerant mass flow kg/hr35.8 33.6 31.9 30.7 29.7 28.9 28.2 27.6 Compressor discharge temperature° C. 110.0 114.4 118.4 121.9 125.1 128.0 130.7 133.2 Evaporator inletpressure bar 0.76 0.81 0.87 0.94 1.02 1.11 1.21 1.31 Condenser inletpressure bar 11.9 13.2 14.6 15.9 17.2 18.5 19.8 21.0 Evaporator inlettemperature ° C. −29.2 29.9 30.6 31.4 32.2 33.0 33.9 −34.8 Evaporatordewpoint ° C. −29.5 −29.0 −28.3 −27.6 −26.8 −26.1 −25.3 −24.6 Evaporatorexit gas temperature ° C. −24.5 −24.0 −23.3 −22.6 −21.8 −21.1 −20.3−19.6 Evaporator mean temperature ° C. −29.3 −29.4 −29.5 −29.5 −29.5−29.5 −29.6 −29.7 Evaporator glide (out-in) K −0.3 0.9 2.3 3.8 5.4 7.08.6 10.2 Compressor suction pressure bar 0.68 0.75 0.82 0.90 0.98 1.081.17 1.28 Compressor discharge pressure bar 11.9 13.2 14.6 15.9 17.218.5 19.8 21.0 Suction line pressure drop Pa/m 416 351 302 265 235 210190 172 Pressure drop relative to reference 142.6% 120.2% 103.5% 90.6%80.3% 71.9% 64.9% 59.0% Condenser dew point ° C. 53.7 55.6 57.2 58.459.3 59.9 60.3 60.5 Condenser bubble point ° C. 52.6 46.6 42.0 38.5 35.833.6 31.9 30.5 Condenser exit liquid temperature ° C. 51.6 45.6 41.037.5 34.8 32.6 30.9 29.5 Condenser mean temperature ° C. 53.2 51.1 49.648.5 47.5 46.8 46.1 45.5 Condenser glide (in-out) K 1.1 9.0 15.2 19.923.6 26.3 28.4 29.9

TABLE 6 Theoretical Performance Data of SelectedR-744/R-1234yf/R-1234ze(E) blends containing 16-30% R-744 and 20%R-1234yf Composition CO₂/R-1234yf/R-1234ze(E) % by weight 

16/20/64 18/20/62 20/20/60 22/20/58 24/20/56 26/20/54 28/20/52 30/20/50COP (heating) 2.19 2.19 2.20 2.20 2.20 2.20 2.20 2.20 COP (heating)relative to Reference 103.7% 104.0% 104.2% 104.3% 104.4% 104.4% 104.3%104.2% Volumetric heating capacity at suction kJ/m³ 1516 1629 1745 18621981 2101 2223 2347 Capacity relative to Reference 172.6% 185.4% 198.6%211.9% 225.5% 239.2% 253.0% 267.1% Critical temperature ° C. 81.39 78.9276.56 74.32 72.18 70.13 68.18 66.31 Critical pressure bar 45.48 46.4047.31 48.21 49.10 49.99 50.87 51.74 Condenser enthalpy change kJ/kg265.4 269.9 274.1 278.1 281.8 285.5 288.9 292.3 Pressure ratio 16.0115.58 15.15 14.74 14.34 13.96 13.60 13.25 Refrigerant mass flow kg/hr27.1 26.7 26.3 25.9 25.5 25.2 24.9 24.6 Compressor discharge temperature° C. 135.5 137.7 139.9 142.0 144.0 146.0 147.9 149.8 Evaporator inletpressure bar 1.41 1.53 1.64 1.77 1.89 2.02 2.16 2.30 Condenser inletpressure bar 22.2 23.4 24.6 25.7 26.9 28.0 29.1 30.2 Evaporator inlettemperature ° C. −35.8 −36.8 −37.8 −38.8 −39.8 −40.8 −41.8 −42.7Evaporator dewpoint ° C. −23.9 −23.3 −22.8 −22.3 −21.8 −21.5 −21.1 −20.9Evaporator exit gas temperature ° C. −18.9 −18.3 −17.8 −17.3 −16.8 −16.5−16.1 −15.9 Evaporator mean temperature ° C. −29.9 −30.0 −30.3 −30.5−30.8 −31.1 −31.4 −31.8 Evaporator glide (out-in) K 11.8 13.4 15.0 16.518.0 19.3 20.6 21.8 Compressor suction pressure bar 1.39 1.50 1.62 1.741.87 2.00 2.14 2.28 Compressor discharge pressure bar 22.2 23.4 24.625.7 26.9 28.0 29.1 30.2 Suction line pressure drop Pa/m 157 145 134 124115 108 101 95 Pressure drop relative to reference 53.9% 49.5% 45.7%42.4% 39.4% 36.8% 34.5% 32.4% Condenser dew point ° C. 60.5 60.3 60.059.6 59.2 58.6 58.0 57.3 Condenser bubble point ° C. 29.4 28.5 27.7 27.126.5 26.1 25.7 25.4 Condenser exit liquid temperature ° C. 28.4 27.526.7 26.1 25.5 25.1 24.7 24.4 Condenser mean temperature ° C. 44.9 44.443.9 43.4 42.9 42.4 41.8 41.3 Condenser glide (in-out) K 31.1 31.8 32.332.6 32.6 32.5 32.2 31.8

TABLE 7 Theoretical Performance Data of SelectedR-744/R-1234yf/R-1234ze(E) blends containing 0-14% R-744 and 30%R-1234yf Composition CO₂/R-1234yf/R-1234ze(E) % by weight 

0/30/70 2/30/68 4/30/66 6/30/64 8/30/62 10/30/60 12/30/58 14/30/56 COP(heating) 1.96 2.02 2.07 2.10 2.12 2.14 2.15 2.16 COP (heating) relativeto Reference 92.8% 95.9% 98.1% 99.7% 100.8% 101.6% 102.1% 102.6%Volumetric heating capacity at suction kJ/m³ 749 847 947 1049 1155 12631374 1488 Capacity relative to Reference 85.2% 96.4% 107.8% 119.4%131.4% 143.7% 156.4% 169.4% Critical temperature ° C. 105.33 101.5197.92 94.53 91.34 88.32 85.46 82.75 Critical pressure bar 37.87 39.0540.20 41.32 42.42 43.50 44.56 45.60 Condenser enthalpy change kJ/kg196.5 210.0 221.1 230.1 237.7 244.1 249.8 254.8 Pressure ratio 16.8017.16 17.30 17.24 17.03 16.72 16.35 15.94 Refrigerant mass flow kg/hr36.6 34.3 32.6 31.3 30.3 29.5 28.8 28.3 Compressor discharge temperature° C. 108.6 113.1 117.1 120.7 123.8 126.7 129.3 131.7 Evaporator inletpressure bar 0.81 0.87 0.93 1.01 1.10 1.20 1.30 1.41 Condenser inletpressure bar 12.5 13.9 15.3 16.7 18.1 19.4 20.7 22.0 Evaporator inlettemperature ° C. −29.2 −29.9 −30.6 −31.4 −32.2 −33.0 −33.8 −34.7Evaporator dewpoint ° C. −29.3 −28.8 −28.2 −27.4 −26.7 −26.0 −25.2 −24.6Evaporator exit gas temperature ° C. −24.3 −23.8 −23.2 −22.4 −21.7 −21.0−20.2 −19.6 Evaporator mean temperature ° C. −29.2 −29.3 −29.4 −29.4−29.4 −29.5 −29.5 −29.6 Evaporator glide (out-in) K −0.1 1.1 2.5 3.9 5.57.0 8.6 10.2 Compressor suction pressure bar 0.74 0.81 0.89 0.97 1.061.16 1.27 1.38 Compressor discharge pressure bar 12.5 13.9 15.3 16.718.1 19.4 20.7 22.0 Suction line pressure drop Pa/m 399 336 289 253 225201 182 165 Pressure drop relative to reference 136.8% 115.0% 99.0%86.7% 76.9% 68.9% 62.2% 56.6% Condenser dew point ° C. 53.8 55.8 57.358.5 59.3 59.9 60.1 60.2 Condenser bubble point ° C. 52.7 46.6 41.9 38.335.6 33.5 31.9 30.6 Condenser exit liquid temperature ° C. 51.7 45.640.9 37.3 34.6 32.5 30.9 29.6 Condenser mean temperature ° C. 53.3 51.249.6 48.4 47.5 46.7 46.0 45.4 Condenser glide (in-out) K 1.1 9.2 15.420.2 23.7 26.3 28.3 29.7

TABLE 8 Theoretical Performance Data of SelectedR-744/R-1234yf/R-1234ze(E) blends containing 16-30% R-744 and 30%R-1234yf Composition CO₂/R-1234yf/R-1234ze(E) % by weight 

16/30/54 18/30/52 20/30/50 22/30/48 24/30/46 26/30/44 28/30/42 30/30/40COP (heating) 2.17 2.17 2.18 2.18 2.18 2.18 2.18 2.18 COP (heating)relative to Reference 102.9% 103.1% 103.3% 103.4% 103.4% 103.4% 103.3%103.2% Volumetric heating capacity at suction kJ/m³ 1605 1724 1847 19712098 2227 2358 2492 Capacity relative to Reference 182.7% 196.3% 210.2%224.3% 238.8% 253.5% 268.4% 283.6% Critical temperature ° C. 80.18 77.7475.41 73.19 71.08 69.06 67.13 65.28 Critical pressure bar 46.62 47.6348.62 49.60 50.57 51.52 52.47 53.40 Condenser enthalpy change kJ/kg259.3 263.4 267.2 270.7 274.1 277.2 280.3 283.1 Pressure ratio 15.5115.07 14.64 14.22 13.81 13.42 13.04 12.68 Refrigerant mass flow kg/hr27.8 27.3 26.9 26.6 26.3 26.0 25.7 25.4 Compressor discharge temperature° C. 133.9 136.0 138.0 140.0 141.8 143.7 145.4 147.2 Evaporator inletpressure bar 1.53 1.65 1.78 1.91 2.05 2.20 2.35 2.51 Condenser inletpressure bar 23.3 24.5 25.7 26.9 28.1 29.3 30.4 31.6 Evaporator inlettemperature ° C. −35.7 −36.6 −37.6 −38.6 −39.6 −40.5 −41.4 −42.3Evaporator dewpoint ° C. −23.9 −23.3 −22.8 −22.3 −21.9 −21.5 −21.2 −20.9Evaporator exit gas temperature ° C. −18.9 −18.3 −17.8 −17.3 −16.9 −16.5−16.2 −15.9 Evaporator mean temperature ° C. −29.8 −30.0 −30.2 −30.4−30.7 −31.0 −31.3 −31.6 Evaporator glide (out-in) K 11.8 13.3 14.8 16.317.7 19.0 20.3 21.4 Compressor suction pressure bar 1.50 1.63 1.76 1.892.03 2.18 2.33 2.49 Compressor discharge pressure bar 23.3 24.5 25.726.9 28.1 29.3 30.4 31.6 Suction line pressure drop Pa/m 151 139 129 119111 104 97 91 Pressure drop relative to reference 51.8% 47.7% 44.0%40.8% 38.0% 35.5% 33.3% 31.2% Condenser dew point ° C. 60.1 59.8 59.559.0 58.4 57.7 57.0 56.2 Condenser bubble point ° C. 29.5 28.7 28.0 27.426.9 26.6 26.3 26.0 Condenser exit liquid temperature ° C. 28.5 27.727.0 26.4 25.9 25.6 25.3 25.0 Condenser mean temperature ° C. 44.8 44.243.7 43.2 42.7 42.1 41.6 41.1 Condenser glide (in-out) K 30.6 31.2 31.531.6 31.4 31.1 30.7 30.1

TABLE 9 Theoretical Performance Data of SelectedR-744/R-1234yf/R-1234ze(E) blends containing 0-14% R-744 and 40%R-1234yf Composition CO₂/R-1234yf/R-1234ze(E) % by weight 

0/40/60 2/40/58 4/40/56 6/40/54 8/40/52 10/40/50 12/40/48 14/40/46 COP(heating) 1.94 2.01 2.06 2.09 2.11 2.13 2.14 2.15 COP (heating) relativeto Reference 92.0% 95.4% 97.6% 99.1% 100.2% 100.9% 101.4% 101.8%Volumetric heating capacity at suction kJ/m³ 789 893 999 1107 1218 13321449 1568 Capacity relative to Reference 89.8% 101.6% 113.7% 126.0%138.7% 151.6% 164.9% 178.5% Critical temperature ° C. 103.81 100.0496.49 93.14 89.99 87.01 84.18 81.51 Critical pressure bar 37.88 39.2140.50 41.75 42.98 44.17 45.34 46.48 Condenser enthalpy change kJ/kg192.1 206.0 217.1 226.1 233.4 239.6 244.9 249.6 Pressure ratio 16.2516.66 16.83 16.80 16.60 16.30 15.93 15.51 Refrigerant mass flow kg/hr37.5 34.9 33.2 31.8 30.8 30.0 29.4 28.8 Compressor discharge temperature° C. 107.4 112.0 116.0 119.6 122.7 125.5 128.1 130.4 Evaporator inletpressure bar 0.86 0.92 1.00 1.08 1.18 1.28 1.39 1.51 Condenser inletpressure bar 13.0 14.5 16.0 17.5 18.9 20.3 21.7 23.0 Evaporator inlettemperature ° C. −29.1 −29.8 −30.6 −31.3 −32.1 −32.9 −33.7 −34.6Evaporator dewpoint ° C. −29.2 −28.7 −28.1 −27.4 −26.7 −26.0 −25.3 −24.6Evaporator exit gas temperature ° C. −24.2 −23.7 −23.1 −22.4 −21.7 −21.0−20.3 −19.6 Evaporator mean temperature ° C. −29.1 −29.3 −29.3 −29.4−29.4 −29.4 −29.5 −29.6 Evaporator glide (out-in) K −0.1 1.1 2.4 3.9 5.46.9 8.4 10.0 Compressor suction pressure bar 0.80 0.87 0.95 1.04 1.141.25 1.36 1.48 Compressor discharge pressure bar 13.0 14.5 16.0 17.518.9 20.3 21.7 23.0 Suction line pressure drop Pa/m 386 323 278 243 216193 175 159 Pressure drop relative to reference 132.1% 110.7% 95.1%83.2% 73.9% 66.2% 59.9% 54.6% Condenser dew point ° C. 53.9 55.9 57.558.6 59.4 59.9 60.1 60.0 Condenser bubble point ° C. 53.0 46.6 41.7 38.135.4 33.3 31.7 30.5 Condenser exit liquid temperature ° C. 52.0 45.640.7 37.1 34.4 32.3 30.7 29.5 Condenser mean temperature ° C. 53.5 51.249.6 48.4 47.4 46.6 45.9 45.3 Condenser glide (in-out) K 0.9 9.3 15.720.5 24.0 26.5 28.3 29.5

TABLE 10 Theoretical Performance Data of SelectedR-744/R-1234yf/R-1234ze(E) blends containing 16-30% R-744 and 40%R-1234yf Composition CO₂/R-1234yf/R-1234ze(E) % by weights 

16/40/44 18/40/42 20/40/40 22/40/38 24/40/36 26/40/34 28/40/32 30/40/30COP (heating) 2.15 2.16 2.16 2.16 2.16 2.16 2.16 2.15 COP (heating)relative to Reference 102.1% 102.3% 102.4% 102.5% 102.4% 102.4% 102.3%102.2% Volumetric heating capacity at suction kJ/m³ 1691 1817 1946 20782213 2350 2491 2634 Capacity relative to Reference 192.5% 206.8% 221.5%236.5% 251.8% 267.5% 283.5% 299.7% Critical temperature ° C. 78.97 76.5674.26 72.07 69.98 67.99 66.08 64.25 Critical pressure bar 47.60 48.7049.78 50.84 51.88 52.91 53.92 54.92 Condenser enthalpy change kJ/kg253.7 257.5 260.9 264.0 266.9 269.6 272.1 274.5 Pressure ratio 15.0814.63 14.19 13.76 13.34 12.93 12.54 12.17 Refrigerant mass flow kg/hr28.4 28.0 27.6 27.3 27.0 26.7 26.5 26.2 Compressor discharge temperature° C. 132.5 134.5 136.4 138.2 139.9 141.5 143.1 144.7 Evaporator inletpressure bar 1.64 1.77 1.91 2.06 2.22 2.38 2.55 2.73 Condenser inletpressure bar 24.3 25.6 26.9 28.1 29.3 30.6 31.8 33.0 Evaporator inlettemperature ° C. −35.5 −36.4 −37.3 −38.3 −39.2 −40.2 −41.1 −41.9Evaporator dewpoint ° C. −23.9 −23.4 −22.8 −22.3 −21.9 −21.5 −21.2 −21.0Evaporator exit gas temperature ° C. −18.9 −18.4 −17.8 −17.3 −16.9 −16.5−16.2 −16.0 Evaporator mean temperature ° C. −29.7 −29.9 −30.1 −30.3−30.6 −30.9 −31.2 −31.5 Evaporator glide (out-in) K 11.5 13.0 14.5 15.917.3 18.6 19.9 21.0 Compressor suction pressure bar 1.61 1.75 1.89 2.042.20 2.36 2.53 2.71 Compressor discharge pressure bar 24.3 25.6 26.928.1 29.3 30.6 31.8 33.0 Suction line pressure drop Pa/m 146 134 124 115107 100 94 88 Pressure drop relative to reference 50.0% 46.0% 42.5%39.5% 36.8% 34.4% 32.2% 30.3% Condenser dew point ° C. 59.8 59.5 59.058.4 57.7 56.9 56.1 55.1 Condenser bubble point ° C. 29.5 28.7 28.1 27.627.2 26.9 26.7 26.5 Condenser exit liquid temperature ° C. 28.5 27.727.1 26.6 26.2 25.9 25.7 25.5 Condenser mean temperature ° C. 44.7 44.143.5 43.0 42.5 41.9 41.4 40.8 Condenser glide (in-out) K 30.3 30.7 30.930.8 30.5 30.0 29.4 28.6

TABLE 11 Theoretical Performance Data of SelectedR-744/R-1234yf/R-1234ze(E) blends containing 0-14% R-744 and 50%R-1234yf Composition CO₂/R-1234yf/R-1234ze(E) % by weight 

0/50/50 2/50/48 4/50/46 6/50/44 8/50/42 10/50/40 12/50/38 14/50/36 COP(heating) 1.93 2.00 2.05 2.08 2.10 2.12 2.13 2.13 COP (heating) relativeto Reference 91.4% 94.9% 97.2% 98.7% 99.7% 100.3% 100.8% 101.1%Volumetric heating capacity at suction kJ/m³ 825 935 1048 1162 1278 13971519 1644 Capacity relative to Reference 93.9% 106.5% 119.2% 132.2%145.4% 159.0% 172.8% 187.0% Critical temperature ° C. 102.30 98.57 95.0691.76 88.64 85.70 82.91 80.27 Critical pressure bar 37.69 39.17 40.6142.00 43.35 44.66 45.94 47.19 Condenser enthalpy change kJ/kg 188.2202.5 213.8 222.8 230.0 235.9 240.9 245.2 Pressure ratio 15.75 16.2316.46 16.45 16.27 15.97 15.60 15.18 Refrigerant mass flow kg/hr 38.335.5 33.7 32.3 31.3 30.5 29.9 29.4 Compressor discharge temperature ° C.106.2 110.9 115.1 118.7 121.8 124.6 127.1 129.3 Evaporator inletpressure bar 0.91 0.98 1.06 1.15 1.25 1.36 1.48 1.61 Condenser inletpressure bar 13.4 15.0 16.6 18.2 19.7 21.2 22.6 24.0 Evaporator inlettemperature ° C. −29.0 −29.7 −30.4 −31.2 −31.9 −32.7 −33.5 −34.3Evaporator dewpoint ° C. −29.2 −28.8 −28.2 −27.5 −26.8 −26.0 −25.3 −24.7Evaporator exit gas temperature ° C. −24.2 −23.8 −23.2 −22.5 −21.8 −21.0−20.3 −19.7 Evaporator mean temperature ° C. −29.1 −29.2 −29.3 −29.3−29.3 −29.4 −29.4 −29.5 Evaporator glide (out-in) K −0.2 1.0 2.3 3.7 5.16.6 8.2 9.7 Compressor suction pressure bar 0.85 0.92 1.01 1.11 1.211.33 1.45 1.58 Compressor discharge pressure bar 13.4 15.0 16.6 18.219.7 21.2 22.6 24.0 Suction line pressure drop Pa/m 375 313 268 234 208187 169 154 Pressure drop relative to reference 128.3% 107.0% 91.7%80.2% 71.2% 63.9% 57.9% 52.8% Condenser dew point ° C. 53.9 56.0 57.658.8 59.6 60.0 60.1 60.0 Condenser bubble point ° C. 53.3 46.5 41.5 37.835.0 33.0 31.4 30.2 Condenser exit liquid temperature ° C. 52.3 45.540.5 36.8 34.0 32.0 30.4 29.2 Condenser mean temperature ° C. 53.6 51.249.5 48.3 47.3 46.5 45.8 45.1 Condenser glide (in-out) K 0.6 9.5 16.221.0 24.5 27.0 28.7 29.7

TABLE 12 Theoretical Performance Data of SelectedR-744/R-1234yf/R-1234ze(E) blends containing 16-30% R-744 and 50%R-1234yf Composition CO₂/R-1234yf/R-1234ze(E) % by weight 

16/50/34 18/50/32 20/50/30 22/50/28 24/50/26 26/50/24 28/50/22 30/50/20COP (heating) 2.14 2.14 2.14 2.14 2.14 2.14 2.14 2.13 COP (heating)relative to Reference 101.4% 101.5% 101.5% 101.6% 101.5% 101.4% 101.3%101.1% Volumetric heating capacity at suction kJ/m³ 1772 1903 2038 21752316 2460 2607 2757 Capacity relative to Reference 201.6% 216.6% 231.9%247.6% 263.6% 280.0% 296.7% 313.7% Critical temperature ° C. 77.76 75.3773.11 70.94 68.88 66.91 65.03 63.23 Critical pressure bar 48.41 49.6050.77 51.91 53.04 54.14 55.23 56.30 Condenser enthalpy change kJ/kg249.0 252.4 255.4 258.1 260.7 263.0 265.1 267.1 Pressure ratio 14.7314.28 13.83 13.39 12.96 12.55 12.16 11.79 Refrigerant mass flow kg/hr28.9 28.5 28.2 27.9 27.6 27.4 27.2 27.0 Compressor discharge temperature° C. 131.3 133.2 135.0 136.7 138.3 139.8 141.3 142.7 Evaporator inletpressure bar 1.74 1.89 2.04 2.20 2.37 2.55 2.73 2.92 Condenser inletpressure bar 25.3 26.6 27.9 29.2 30.5 31.8 33.0 34.3 Evaporator inlettemperature ° C. −35.2 −36.1 −37.1 −38.0 −39.0 −39.9 −40.9 −41.8Evaporator dewpoint ° C. −24.0 −23.4 −22.9 −22.4 −21.9 −21.6 −21.2 −21.0Evaporator exit gas temperature ° C. −19.0 −18.4 −17.9 −17.4 −16.9 −16.6−16.2 −16.0 Evaporator mean temperature ° C. −29.6 −29.8 −30.0 −30.2−30.5 −30.7 −31.0 −31.4 Evaporator glide (out-in) K 11.2 12.7 14.2 15.617.0 18.4 19.6 20.8 Compressor suction pressure bar 1.72 1.87 2.02 2.182.35 2.53 2.72 2.91 Compressor discharge pressure bar 25.3 26.6 27.929.2 30.5 31.8 33.0 34.3 Suction line pressure drop Pa/m 141 130 121 112104 98 92 86 Pressure drop relative to reference 48.4% 44.6% 41.3% 38.4%35.8% 33.4% 31.4% 29.5% Condenser dew point ° C. 59.7 59.2 58.7 58.057.2 56.3 55.3 54.3 Condenser bubble point ° C. 29.3 28.6 28.1 27.6 27.327.1 26.9 26.8 Condenser exit liquid temperature ° C. 28.3 27.6 27.126.6 26.3 26.1 25.9 25.8 Condenser mean temperature ° C. 44.5 43.9 43.442.8 42.2 41.7 41.1 40.5 Condenser glide (in-out) K 30.4 30.6 30.6 30.329.8 29.2 28.4 27.5

TABLE 13 Theoretical Performance Data of SelectedR-744/R-1234yf/R-1234ze(E) blends containing 0-14% R-744 and 60%R-1234yf Composition CO₂/R-1234yf/R-1234ze(E) % by weight 

0/60/40 2/60/38 4/60/36 6/60/34 8/60/32 10/60/30 12/60/28 14/60/26 COP(heating) 1.91 1.99 2.04 2.07 2.09 2.11 2.11 2.12 COP (heating) relativeto Reference 90.7% 94.4% 96.8% 98.3% 99.3% 99.9% 100.3% 100.5%Volumetric heating capacity at suction kJ/m³ 855 973 1091 1211 1332 14551581 1710 Capacity relative to Reference 97.4% 110.7% 124.2% 137.8%151.6% 165.6% 179.9% 194.6% Critical temperature ° C. 100.78 97.09 93.6390.37 87.29 84.39 81.63 79.02 Critical pressure bar 37.30 38.94 40.5242.05 43.53 44.97 46.37 47.72 Condenser enthalpy change kJ/kg 184.7199.8 211.4 220.3 227.4 233.1 237.8 241.9 Pressure ratio 15.33 15.9016.19 16.21 16.05 15.76 15.38 14.96 Refrigerant mass flow kg/hr 39.036.0 34.1 32.7 31.7 30.9 30.3 29.8 Compressor discharge temperature ° C.105.1 110.1 114.4 118.1 121.2 124.0 126.4 128.6 Evaporator inletpressure bar 0.96 1.03 1.11 1.20 1.31 1.43 1.55 1.69 Condenser inletpressure bar 13.8 15.5 17.2 18.9 20.5 22.0 23.5 24.9 Evaporator inlettemperature ° C. −28.9 −29.6 −30.3 −31.0 −31.8 −32.5 −33.4 −34.2Evaporator dewpoint ° C. −29.2 −28.8 −28.3 −27.6 −26.9 −26.1 −25.4 −24.7Evaporator exit gas temperature ° C. −24.2 −23.8 −23.3 −22.6 −21.9 −21.1−20.4 −19.7 Evaporator mean temperature ° C. −29.0 −29.2 −29.3 −29.3−29.3 −29.3 −29.4 −29.4 Evaporator glide (out-in) K −0.3 0.8 2.0 3.4 4.96.4 8.0 9.5 Compressor suction pressure bar 0.90 0.97 1.06 1.16 1.281.40 1.53 1.66 Compressor discharge pressure bar 13.8 15.5 17.2 18.920.5 22.0 23.5 24.9 Suction line pressure drop Pa/m 366 304 259 227 201181 164 150 Pressure drop relative to reference 125.4% 104.0% 88.8%77.6% 68.9% 61.9% 56.1% 51.3% Condenser dew point ° C. 53.9 56.2 57.959.1 59.9 60.2 60.3 60.1 Condenser bubble point ° C. 53.5 46.3 41.0 37.234.5 32.4 30.9 29.8 Condenser exit liquid temperature ° C. 52.5 45.340.0 36.2 33.5 31.4 29.9 28.8 Condenser mean temperature ° C. 53.7 51.249.5 48.2 47.2 46.3 45.6 45.0 Condenser glide (in-out) K 0.4 9.9 16.921.9 25.4 27.8 29.4 30.4

TABLE 14 Theoretical Performance Data of SelectedR-744/R-1234yf/R-1234ze(E) blends containing 16-30% R-744 and 60%R-1234yf Composition CO₂/R-1234yf/R-1234ze(E) % by weight 

16/60/24 18/60/22 20/60/20 22/60/18 24/60/16 26/60/14 28/60/12 30/60/10COP (heating) 2.12 2.12 2.12 2.12 2.12 2.12 2.11 2.11 COP (heating)relative to Reference 100.7% 100.7% 100.7% 100.7% 100.6% 100.4% 100.2%100.0% Volumetric heating capacity at suction kJ/m³ 1841 1976 2114 22542398 2544 2692 2842 Capacity relative to Reference 209.5% 224.9% 240.5%256.6% 272.9% 289.5% 306.4% 323.5% Critical temperature ° C. 76.55 74.1971.95 69.82 67.78 65.84 63.98 62.20 Critical pressure bar 49.05 50.3451.60 52.84 54.05 55.23 56.39 57.53 Condenser enthalpy change kJ/kg245.4 248.4 251.2 253.6 255.9 257.9 259.8 261.5 Pressure ratio 14.5214.06 13.61 13.17 12.74 12.33 11.95 11.58 Refrigerant mass flow kg/hr29.3 29.0 28.7 28.4 28.1 27.9 27.7 27.5 Compressor discharge temperature° C. 130.6 132.4 134.1 135.7 137.2 138.7 140.1 141.5 Evaporator inletpressure bar 1.83 1.99 2.15 2.32 2.50 2.68 2.87 3.07 Condenser inletpressure bar 26.3 27.6 29.0 30.3 31.6 32.9 34.1 35.4 Evaporator inlettemperature ° C. −35.1 −36.0 −36.9 −37.9 −38.9 −39.9 −40.9 −42.0Evaporator dewpoint ° C. −24.0 −23.4 −22.9 −22.4 −21.9 −21.5 −21.1 −20.9Evaporator exit gas temperature ° C. −19.0 −18.4 −17.9 −17.4 −16.9 −16.5−16.1 −15.9 Evaporator mean temperature ° C. −29.5 −29.7 −29.9 −30.1−30.4 −30.7 −31.0 −31.4 Evaporator glide (out-in) K 11.0 12.5 14.0 15.517.0 18.4 19.8 21.1 Compressor suction pressure bar 1.81 1.97 2.13 2.302.48 2.66 2.86 3.06 Compressor discharge pressure bar 26.3 27.6 29.030.3 31.6 32.9 34.1 35.4 Suction line pressure drop Pa/m 138 127 118 110102 96 90 85 Pressure drop relative to reference 47.1% 43.5% 40.3% 37.5%35.0% 32.8% 30.8% 29.1% Condenser dew point ° C. 59.8 59.2 58.5 57.756.8 55.8 54.8 53.6 Condenser bubble point ° C. 28.9 28.2 27.7 27.4 27.126.9 26.8 26.7 Condenser exit liquid temperature ° C. 27.9 27.2 26.726.4 26.1 25.9 25.8 25.7 Condenser mean temperature ° C. 44.3 43.7 43.142.6 42.0 41.4 40.8 40.1 Condenser glide (in-out) K 30.9 31.0 30.8 30.429.7 28.9 28.0 26.9

TABLE 15 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 0-14% R-744 and 5% R-1243zfComposition CO₂/R-1243zf/R-1234ze(E) % by weight 

0/5/95 2/5/93 4/5/91 6/5/89 8/5/97 10/5/85 12/5/83 14/5/81 COP (heating)1.99 2.05 2.10 2.13 2.16 2.18 2.20 2.21 COP relative to Reference 94.5%97.4% 99.6% 101.2% 102.5% 103.4% 104.2% 104.8% Volumetric heatingcapacity at suction kJ/m3 628 708 791 877 966 1058 1153 1251 Capacityrelative to Reference 71.5% 80.6% 90.0% 99.8% 110.0% 120.4% 131.2%142.4% Critical temperature ° C. 109.58 105.66 101.97 98.50 95.22 92.1289.19 86.40 Critical pressure bar 36.65 37.39 38.14 38.88 39.62 40.3741.11 41.85 Condenser enthalpy change kJ/kg 211.1 224.3 235.5 245.1253.4 260.8 267.4 273.5 Pressure ratio 18.46 18.68 18.72 18.62 18.3818.07 17.70 17.30 Refrigerant mass flow kg/hr 34.1 32.1 30.6 29.4 28.427.6 26.9 26.3 Compressor discharge temperature ° C. 112.8 117.1 120.9124.5 127.7 130.7 133.5 136.1 Evaporator inlet pressure bar 0.66 0.710.76 0.82 0.89 0.96 1.04 1.13 Condenser inlet pressure bar 10.8 12.013.2 14.3 15.5 16.7 17.8 18.9 Evaporator inlet temperature ° C. −29.0−29.7 −30.3 −31.1 −31.8 −32.7 −33.5 −34.5 Evaporator dewpoint ° C. −30.2−29.6 −29.0 −28.2 −27.5 −26.7 −25.9 −25.1 Evaporator exit gastemperature ° C. −25.2 −24.6 −24.0 −23.2 −22.5 −21.7 −20.9 −20.1Evaporator mean temperature ° C. −29.6 −29.6 −29.7 −29.7 −29.6 −29.7−29.7 −29.8 Evaporator glide (out-in) K −1.2 0.0 1.4 2.8 4.4 6.0 7.6 9.3Compressor suction pressure bar 0.59 0.64 0.70 0.77 0.84 0.92 1.01 1.09Compressor discharge pressure bar 10.8 12.0 13.2 14.3 15.5 16.7 17.818.9 Suction line pressure drop Pa/m 451 382 330 289 256 229 206 187Pressure drop relative to reference 154.5% 131.0% 113.0% 99.0% 87.6%78.3% 70.5% 63.9% Condenser dew point ° C. 53.1 55.0 56.6 57.9 58.9 59.760.2 60.6 Condenser bubble point ° C. 52.9 47.3 42.8 39.3 36.4 34.2 32.330.8 Condenser exit liquid temperature ° C. 51.9 46.3 41.8 38.3 35.433.2 31.3 29.8 Condenser mean temperature ° C. 53.0 51.1 49.7 48.6 47.746.9 46.3 45.7 Condenser glide (in-out) K 0.2 7.7 13.8 18.6 22.4 25.527.9 29.9

TABLE 16 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 16-30% R-744 and 5%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

16/5/79 18/5/77 20/5/75 22/5/73 24/5/71 26/5/69 28/5/67 30/5/65 COP(heating) 2.22 2.23 2.23 2.24 2.24 2.24 2.24 2.24 COP relative toReference 105.3% 105.7% 106.0% 106.2% 106.3% 106.4% 106.4% 106.3%Volumetric heating capacity at suction kJ/m3 1351 1453 1557 1663 17691876 1984 2092 Capacity relative to Reference 153.8% 165.4% 177.2%189.2% 201.3% 213.5% 225.8% 238.1% Critical temperature ° C. 83.76 81.2478.85 76.57 74.39 72.31 70.32 68.42 Critical pressure bar 42.59 43.3444.08 44.82 45.56 46.31 47.05 47.79 Condenser enthalpy change kJ/kg279.1 284.3 289.2 294.0 298.5 302.9 307.2 311.4 Pressure ratio 16.8816.46 16.05 15.65 15.26 14.90 14.55 14.23 Refrigerant mass flow kg/hr25.8 25.3 24.9 24.5 24.1 23.8 23.4 23.1 Compressor discharge temperature° C. 138.7 141.1 143.4 145.7 147.9 150.2 152.4 154.6 Evaporator inletpressure bar 1.22 1.31 1.41 1.51 1.62 1.72 1.83 1.95 Condenser inletpressure bar 20.0 21.1 22.2 23.3 24.3 25.4 26.4 27.4 Evaporator inlettemperature ° C. −35.4 −36.4 −37.4 −38.5 −39.5 −40.5 −41.5 −42.5Evaporator dewpoint ° C. −24.4 −23.8 −23.2 −22.6 −22.1 −21.7 −21.3 −21.0Evaporator exit gas temperature ° C. −19.4 −18.8 −18.2 −17.6 −17.1 −16.7−16.3 −16.0 Evaporator mean temperature ° C. −29.9 −30.1 −30.3 −30.5−30.8 −31.1 −31.4 −31.8 Evaporator glide (out-in) K 11.0 12.6 14.3 15.817.4 18.8 20.2 21.5 Compressor suction pressure bar 1.19 1.28 1.39 1.491.59 1.70 1.81 1.93 Compressor discharge pressure bar 20.0 21.1 22.223.3 24.3 25.4 26.4 27.4 Suction line pressure drop Pa/m 170 156 144 133124 115 108 101 Pressure drop relative to reference 58.3% 53.4% 49.2%45.5% 42.3% 39.4% 36.9% 34.6% Condenser dew point ° C. 60.8 60.9 60.960.7 60.5 60.1 59.7 59.3 Condenser bubble point ° C. 29.5 28.4 27.5 26.726.0 25.4 24.9 24.5 Condenser exit liquid temperature ° C. 28.5 27.426.5 25.7 25.0 24.4 23.9 23.5 Condenser mean temperature ° C. 45.2 44.744.2 43.7 43.2 42.8 42.3 41.9 Condenser glide (in-out) K 31.4 32.5 33.434.0 34.5 34.7 34.8 34.8

TABLE 17 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 0-14% R-744 and 10%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

0/10/90 2/10/88 4/10/86 6/10/84 8/10/82 10/10/80 12/10/78 14/10/76 COP(heating) 2.00 2.05 2.10 2.13 2.16 2.18 2.20 2.21 COP relative toReference 94.8% 97.4% 99.5% 101.2% 102.4% 103.4% 104.2% 104.8%Volumetric heating capacity at suction kJ/m3 641 721 803 889 978 10701165 1263 Capacity relative to Reference 73.0% 82.0% 91.4% 101.1% 111.3%121.8% 132.6% 143.7% Critical temperature ° C. 109.27 105.40 101.7598.32 95.07 92.00 89.09 86.33 Critical pressure bar 36.72 37.44 38.1538.88 39.60 40.32 41.05 41.77 Condenser enthalpy change kJ/kg 212.1224.9 236.0 245.5 253.8 261.2 267.8 273.9 Pressure ratio 18.10 18.3818.41 18.31 18.07 17.77 17.42 17.03 Refrigerant mass flow kg/hr 33.932.0 30.5 29.3 28.4 27.6 26.9 26.3 Compressor discharge temperature ° C.112.7 117.0 120.8 124.3 127.5 130.5 133.3 135.9 Evaporator inletpressure bar 0.68 0.72 0.77 0.83 0.90 0.98 1.06 1.14 Condenser inletpressure bar 10.9 12.1 13.2 14.4 15.5 16.7 17.8 18.9 Evaporator inlettemperature ° C. −29.0 −29.7 −30.4 −31.1 −31.8 −32.6 −33.5 −34.4Evaporator dewpoint ° C. −30.1 −29.6 −29.0 −28.2 −27.5 −26.7 −25.9 −25.2Evaporator exit gas temperature ° C. −25.1 −24.6 −24.0 −23.2 −22.5 −21.7−20.9 −20.2 Evaporator mean temperature ° C. −29.6 −29.6 −29.7 −29.7−29.6 −29.7 −29.7 −29.8 Evaporator glide (out-in) K −1.1 0.1 1.4 2.8 4.45.9 7.5 9.2 Compressor suction pressure bar 0.60 0.66 0.72 0.79 0.860.94 1.02 1.11 Compressor discharge pressure bar 10.9 12.1 13.2 14.415.5 16.7 17.8 18.9 Suction line pressure drop Pa/m 441 375 325 285 252226 204 185 Pressure drop relative to reference 150.8% 128.4% 111.1%97.5% 86.4% 77.3% 69.7% 63.2% Condenser dew point ° C. 52.9 54.9 56.457.6 58.6 59.4 59.9 60.3 Condenser bubble point ° C. 52.6 47.4 43.0 39.636.8 34.5 32.7 31.1 Condenser exit liquid temperature ° C. 51.6 46.442.0 38.6 35.8 33.5 31.7 30.1 Condenser mean temperature ° C. 52.8 51.149.7 48.6 47.7 46.9 46.3 45.7 Condenser glide (in-out) K 0.2 7.5 13.418.1 21.8 24.9 27.3 29.2

TABLE 18 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 16-30% R-744 and 10%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

16/10/74 18/10/72 20/10/70 22/10/68 24/10/66 26/10/64 28/10/62 30/10/60COP (heating) 2.22 2.23 2.24 2.24 2.24 2.24 2.25 2.24 COP relative toReference 105.3% 105.7% 106.0% 106.2% 106.4% 106.5% 106.5% 106.4%Volumetric heating capacity at suction kJ/m3 1363 1465 1569 1675 17821889 1998 2107 Capacity relative to Reference 155.1% 166.7% 178.6%190.6% 202.8% 215.0% 227.4% 239.8% Critical temperature ° C. 83.70 81.2178.83 76.57 74.40 72.34 70.36 68.47 Critical pressure bar 42.50 43.2243.95 44.68 45.41 46.13 46.86 47.59 Condenser enthalpy change kJ/kg279.5 284.7 289.7 294.4 299.0 303.4 307.7 311.8 Pressure ratio 16.6216.22 15.82 15.43 15.05 14.70 14.36 14.03 Refrigerant mass flow kg/hr25.8 25.3 24.9 24.5 24.1 23.7 23.4 23.1 Compressor discharge temperature° C. 138.4 140.7 143.1 145.3 147.5 149.7 151.9 154.1 Evaporator inletpressure bar 1.23 1.33 1.43 1.53 1.63 1.74 1.85 1.97 Condenser inletpressure bar 20.0 21.1 22.2 23.2 24.3 25.3 26.4 27.4 Evaporator inlettemperature ° C. −35.3 −36.3 −37.2 −38.2 −39.2 −40.2 −41.2 −42.1Evaporator dewpoint ° C. −24.5 −23.9 −23.3 −22.7 −22.2 −21.8 −21.4 −21.1Evaporator exit gas temperature ° C. −19.5 −18.9 −18.3 −17.7 −17.2 −16.8−16.4 −16.1 Evaporator mean temperature ° C. −29.9 −30.1 −30.3 −30.5−30.7 −31.0 −31.3 −31.6 Evaporator glide (out-in) K 10.8 12.4 14.0 15.517.0 18.4 19.8 21.0 Compressor suction pressure bar 1.20 1.30 1.40 1.511.61 1.72 1.84 1.95 Compressor discharge pressure bar 20.0 21.1 22.223.2 24.3 25.3 26.4 27.4 Suction line pressure drop Pa/m 169 155 142 132123 114 107 100 Pressure drop relative to reference 57.7% 52.9% 48.8%45.1% 42.0% 39.1% 36.6% 34.4% Condenser dew point ° C. 60.5 60.6 60.660.4 60.2 59.9 59.5 59.1 Condenser bubble point ° C. 29.8 28.7 27.8 27.026.3 25.7 25.2 24.8 Condenser exit liquid temperature ° C. 28.8 27.726.8 26.0 25.3 24.7 24.2 23.8 Condenser mean temperature ° C. 45.2 44.744.2 43.7 43.3 42.8 42.4 41.9 Condenser glide (in-out) K 30.7 31.9 32.833.4 33.9 34.2 34.3 34.3

TABLE 19 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 0-14% R-744 and 15%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

0/15/85 2/15/83 4/15/81 6/15/79 8/15/77 10/15/75 12/15/73 14/15/71 COP(heating) 2.00 2.05 2.10 2.13 2.16 2.18 2.20 2.21 COP relative toReference 94.6% 97.4% 99.5% 101.1% 102.4% 103.4% 104.1% 104.8%Volumetric heating capacity at suction kJ/m3 653 733 815 900 989 10811176 1274 Capacity relative to Reference 74.4% 83.4% 92.8% 102.4% 112.6%123.0% 133.8% 144.9% Critical temperature ° C. 108.97 105.14 101.5498.13 94.92 91.87 88.99 86.25 Critical pressure bar 36.76 37.46 38.1638.86 39.56 40.27 40.97 41.68 Condenser enthalpy change kJ/kg 212.8225.5 236.5 246.0 254.2 261.6 268.3 274.3 Pressure ratio 17.92 18.1018.12 18.02 17.79 17.50 17.15 16.77 Refrigerant mass flow kg/hr 33.831.9 30.4 29.3 28.3 27.5 26.8 26.2 Compressor discharge temperature ° C.112.9 117.0 120.7 124.2 127.3 130.3 133.0 135.6 Evaporator inletpressure bar 0.69 0.73 0.79 0.85 0.92 0.99 1.07 1.16 Condenser inletpressure bar 11.0 12.2 13.3 14.4 15.6 16.7 17.8 18.9 Evaporator inlettemperature ° C. −29.1 −29.7 −30.4 −31.1 −31.8 −32.6 −33.4 −34.3Evaporator dewpoint ° C. −30.1 −29.6 −28.9 −28.2 −27.5 −26.7 −26.0 −25.3Evaporator exit gas temperature ° C. −25.1 −24.6 −23.9 −23.2 −22.5 −21.7−21.0 −20.3 Evaporator mean temperature ° C. −29.6 −29.6 −29.6 −29.7−29.6 −29.7 −29.7 −29.8 Evaporator glide (out-in) K −1.0 0.1 1.4 2.8 4.35.9 7.4 9.0 Compressor suction pressure bar 0.62 0.67 0.73 0.80 0.880.95 1.04 1.13 Compressor discharge pressure bar 11.0 12.2 13.3 14.415.6 16.7 17.8 18.9 Suction line pressure drop Pa/m 431 368 319 281 249223 201 183 Pressure drop relative to reference 147.6% 126.0% 109.3%96.1% 85.3% 76.4% 68.9% 62.6% Condenser dew point ° C. 53.1 54.8 56.257.4 58.4 59.1 59.7 60.0 Condenser bubble point ° C. 52.8 47.5 43.3 39.837.1 34.8 33.0 31.5 Condenser exit liquid temperature ° C. 51.8 46.542.3 38.8 36.1 33.8 32.0 30.5 Condenser mean temperature ° C. 52.9 51.149.7 48.6 47.7 47.0 46.3 45.7 Condenser glide (in-out) K 0.3 7.3 13.017.6 21.3 24.3 26.7 28.6

TABLE 20 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 16-30% R-744 and 15%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

16/15/69 18/15/67 20/15/65 22/15/63 24/15/61 26/15/59 28/15/57 30/15/55COP (heating) 2.22 2.23 2.24 2.24 2.24 2.25 2.25 2.25 COP relative toReference 105.3% 105.7% 106.0% 106.3% 106.4% 106.5% 106.6% 106.5%Volumetric heating capacity at suction kJ/m3 1374 1476 1580 1686 17931902 2011 2121 Capacity relative to Reference 156.3% 168.0% 179.9%191.9% 204.1% 216.4% 228.9% 241.4% Critical temperature ° C. 83.65 81.1778.81 76.56 74.42 72.36 70.40 68.52 Critical pressure bar 42.39 43.1043.81 44.53 45.24 45.95 46.67 47.38 Condenser enthalpy change kJ/kg280.0 285.2 290.2 295.0 299.5 303.9 308.2 312.4 Pressure ratio 16.3815.99 15.60 15.22 14.85 14.50 14.17 13.85 Refrigerant mass flow kg/hr25.7 25.2 24.8 24.4 24.0 23.7 23.4 23.0 Compressor discharge temperature° C. 138.1 140.5 142.7 145.0 147.2 149.4 151.5 153.6 Evaporator inletpressure bar 1.25 1.34 1.44 1.55 1.65 1.76 1.87 1.99 Condenser inletpressure bar 20.0 21.1 22.1 23.2 24.2 25.3 26.3 27.3 Evaporator inlettemperature ° C. −35.2 −36.1 −37.1 −38.0 −39.0 −40.0 −40.9 −41.8Evaporator dewpoint ° C. −24.6 −24.0 −23.4 −22.8 −22.4 −21.9 −21.6 −21.3Evaporator exit gas temperature ° C. −19.6 −19.0 −18.4 −17.8 −17.4 −16.9−16.6 −16.3 Evaporator mean temperature ° C. −29.9 −30.0 −30.2 −30.4−30.7 −30.9 −31.2 −31.5 Evaporator glide (out-in) K 10.6 12.2 13.7 15.216.6 18.0 19.3 20.5 Compressor suction pressure bar 1.22 1.32 1.42 1.521.63 1.74 1.86 1.97 Compressor discharge pressure bar 20.0 21.1 22.123.2 24.2 25.3 26.3 27.3 Suction line pressure drop Pa/m 167 153 141 131122 113 106 100 Pressure drop relative to reference 57.2% 52.5% 48.4%44.8% 41.6% 38.8% 36.3% 34.1% Condenser dew point ° C. 60.3 60.3 60.360.2 60.0 59.7 59.3 58.9 Condenser bubble point ° C. 30.2 29.1 28.1 27.326.6 26.0 25.5 25.1 Condenser exit liquid temperature ° C. 29.2 28.127.1 26.3 25.6 25.0 24.5 24.1 Condenser mean temperature ° C. 45.2 44.744.2 43.8 43.3 42.9 42.4 42.0 Condenser glide (in-out) K 30.1 31.3 32.232.9 33.3 33.6 33.8 33.8

TABLE 21 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 0-14% R-744 and 20%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

0/20/80 2/20/78 4/20/76 6/20/74 8/20/72 10/20/70 12/20/68 14/20/66 COP(heating) 2.00 2.05 2.10 2.13 2.16 2.18 2.20 2.21 COP relative toReference 94.7% 97.4% 99.5% 101.1% 102.3% 103.3% 104.1% 104.8%Volumetric heating capacity at suction kJ/m3 665 744 826 912 1000 10921187 1284 Capacity relative to Reference 75.7% 84.7% 94.0% 103.7% 113.8%124.3% 135.0% 146.1% Critical temperature ° C. 108.68 104.89 101.3297.95 94.77 91.75 88.89 86.18 Critical pressure bar 36.79 37.47 38.1538.83 39.51 40.20 40.89 41.58 Condenser enthalpy change kJ/kg 213.7226.3 237.1 246.5 254.8 262.1 268.8 274.9 Pressure ratio 17.67 17.8317.85 17.74 17.52 17.24 16.90 16.54 Refrigerant mass flow kg/hr 33.731.8 30.4 29.2 28.3 27.5 26.8 26.2 Compressor discharge temperature ° C.113.0 117.0 120.7 124.1 127.2 130.1 132.8 135.4 Evaporator inletpressure bar 0.70 0.75 0.80 0.86 0.93 1.01 1.09 1.17 Condenser inletpressure bar 11.1 12.2 13.4 14.5 15.6 16.7 17.8 18.9 Evaporator inlettemperature ° C. −29.1 −29.7 −30.4 −31.1 −31.8 −32.5 −33.4 −34.2Evaporator dewpoint ° C. −30.0 −29.5 −28.9 −28.2 −27.5 −26.8 −26.1 −25.3Evaporator exit gas temperature ° C. −25.0 −24.5 −23.9 −23.2 −22.5 −21.8−21.1 −20.3 Evaporator mean temperature ° C. −29.6 −29.6 −29.6 −29.6−29.6 −29.7 −29.7 −29.8 Evaporator glide (out-in) K −0.9 0.2 1.5 2.8 4.35.8 7.3 8.9 Compressor suction pressure bar 0.63 0.69 0.75 0.82 0.890.97 1.05 1.14 Compressor discharge pressure bar 11.1 12.2 13.4 14.515.6 16.7 17.8 18.9 Suction line pressure drop Pa/m 422 361 314 277 246221 199 181 Pressure drop relative to reference 144.5% 123.7% 107.6%94.8% 84.3% 75.6% 68.2% 62.0% Condenser dew point ° C. 53.0 54.7 56.157.2 58.1 58.9 59.4 59.8 Condenser bubble point ° C. 52.8 47.6 43.5 40.137.4 35.2 33.3 31.8 Condenser exit liquid temperature ° C. 51.8 46.642.5 39.1 36.4 34.2 32.3 30.8 Condenser mean temperature ° C. 52.9 51.149.8 48.7 47.8 47.0 46.4 45.8 Condenser glide (in-out) K 0.3 7.1 12.617.1 20.8 23.7 26.1 28.0

TABLE 22 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 16-30% R-744 and 20%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

16/20/64 18/20/62 20/20/60 22/20/58 24/20/56 26/20/54 28/20/52 30/20/50COP (heating) 2.22 2.23 2.24 2.24 2.24 2.25 2.25 2.25 COP relative toReference 105.3% 105.7% 106.0% 106.3% 106.5% 106.6% 106.6% 106.7%Volumetric heating capacity at suction kJ/m3 1384 1486 1591 1697 18041913 2023 2134 Capacity relative to Reference 157.5% 169.2% 181.0%193.1% 205.3% 217.7% 230.2% 242.8% Critical temperature ° C. 83.60 81.1478.80 76.56 74.43 72.39 70.44 68.57 Critical pressure bar 42.28 42.9743.67 44.37 45.07 45.77 46.47 47.17 Condenser enthalpy change kJ/kg280.5 285.8 290.8 295.6 300.2 304.6 308.9 313.0 Pressure ratio 16.1615.78 15.40 15.03 14.67 14.33 14.00 13.68 Refrigerant mass flow kg/hr25.7 25.2 24.8 24.4 24.0 23.6 23.3 23.0 Compressor discharge temperature° C. 137.8 140.2 142.5 144.7 146.9 149.0 151.1 153.2 Evaporator inletpressure bar 1.26 1.36 1.46 1.56 1.67 1.78 1.89 2.01 Condenser inletpressure bar 20.0 21.0 22.1 23.1 24.2 25.2 26.2 27.2 Evaporator inlettemperature ° C. −35.1 −36.0 −36.9 −37.8 −38.8 −39.7 −40.6 −41.5Evaporator dewpoint ° C. −24.7 −24.1 −23.5 −22.9 −22.5 −22.1 −21.7 −21.4Evaporator exit gas temperature ° C. −19.7 −19.1 −18.5 −17.9 −17.5 −17.1−16.7 −16.4 Evaporator mean temperature ° C. −29.9 −30.0 −30.2 −30.4−30.6 −30.9 −31.1 −31.4 Evaporator glide (out-in) K 10.4 11.9 13.4 14.916.3 17.6 18.9 20.1 Compressor suction pressure bar 1.24 1.33 1.44 1.541.65 1.76 1.87 1.99 Compressor discharge pressure bar 20.0 21.0 22.123.1 24.2 25.2 26.2 27.2 Suction line pressure drop Pa/m 165 152 140 130121 113 105 99 Pressure drop relative to reference 56.6% 52.0% 48.0%44.4% 41.3% 38.5% 36.1% 33.8% Condenser dew point ° C. 60.0 60.1 60.160.0 59.8 59.5 59.1 58.7 Condenser bubble point ° C. 30.5 29.4 28.4 27.626.9 26.3 25.8 25.3 Condenser exit liquid temperature ° C. 29.5 28.427.4 26.6 25.9 25.3 24.8 24.3 Condenser mean temperature ° C. 45.2 44.744.3 43.8 43.3 42.9 42.5 42.0 Condenser glide (in-out) K 29.5 30.7 31.632.3 32.8 33.2 33.3 33.4

TABLE 23 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 0-14% R-744 and 25%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

0/25/75 2/25/73 4/25/71 6/25/69 8/25/67 10/25/65 12/25/63 14/25/61 COP(heating) 2.00 2.05 2.10 2.13 2.16 2.18 2.19 2.21 COP relative toReference 94.8% 97.4% 99.5% 101.0% 102.3% 103.3% 104.1% 104.7%Volumetric heating capacity at suction kJ/m3 677 756 837 922 1011 11021197 1294 Capacity relative to Reference 77.0% 86.0% 95.3% 105.0% 115.0%125.4% 136.2% 147.3% Critical temperature ° C. 108.39 104.64 101.1197.77 94.62 91.63 88.80 86.10 Critical pressure bar 36.81 37.46 38.1238.78 39.45 40.12 40.80 41.47 Condenser enthalpy change kJ/kg 214.6227.0 237.7 247.1 255.3 262.7 269.4 275.5 Pressure ratio 17.44 17.5817.59 17.48 17.27 16.99 16.67 16.32 Refrigerant mass flow kg/hr 33.531.7 30.3 29.1 28.2 27.4 26.7 26.1 Compressor discharge temperature ° C.113.0 117.0 120.6 124.0 127.1 129.9 132.6 135.2 Evaporator inletpressure bar 0.71 0.76 0.81 0.88 0.95 1.02 1.10 1.19 Condenser inletpressure bar 11.2 12.3 13.4 14.5 15.6 16.7 17.8 18.9 Evaporator inlettemperature ° C. −29.1 −29.7 −30.4 −31.0 −31.7 −32.5 −33.3 −34.1Evaporator dewpoint ° C. −30.0 −29.5 −28.9 −28.2 −27.5 −26.8 −26.1 −25.4Evaporator exit gas temperature ° C. −25.0 −24.5 −23.9 −23.2 −22.5 −21.8−21.1 −20.4 Evaporator mean temperature ° C. −29.6 −29.6 −29.6 −29.6−29.6 −29.7 −29.7 −29.8 Evaporator glide (out-in) K −0.9 0.2 1.5 2.8 4.25.7 7.2 8.7 Compressor suction pressure bar 0.64 0.70 0.76 0.83 0.900.98 1.07 1.16 Compressor discharge pressure bar 11.2 12.3 13.4 14.515.6 16.7 17.8 18.9 Suction line pressure drop Pa/m 413 355 310 273 243218 197 179 Pressure drop relative to reference 141.5% 121.6% 106.0%93.5% 83.3% 74.7% 67.5% 61.4% Condenser dew point ° C. 53.0 54.6 55.957.0 57.9 58.6 59.2 59.5 Condenser bubble point ° C. 52.7 47.7 43.6 40.437.7 35.5 33.6 32.1 Condenser exit liquid temperature ° C. 51.7 46.742.6 39.4 36.7 34.5 32.6 31.1 Condenser mean temperature ° C. 52.9 51.149.8 48.7 47.8 47.0 46.4 45.8 Condenser glide (in-out) K 0.3 6.9 12.316.7 20.3 23.2 25.5 27.4

TABLE 24 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 16-30% R-744 and 25%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

16/25/59 18/25/57 20/25/55 22/25/53 24/25/51 26/25/49 28/25/47 30/25/45COP (heating) 2.22 2.23 2.24 2.24 2.25 2.25 2.25 2.25 COP relative toReference 105.3% 105.7% 106.1% 106.3% 106.5% 106.6% 106.7% 106.8%Volumetric heating capacity at suction kJ/m3 1394 1496 1601 1707 18141923 2033 2145 Capacity relative to Reference 158.6% 170.3% 182.2%194.2% 206.5% 218.9% 231.4% 244.1% Critical temperature ° C. 83.54 81.1178.78 76.56 74.44 72.41 70.47 68.61 Critical pressure bar 42.15 42.8343.52 44.20 44.89 45.58 46.27 46.96 Condenser enthalpy change kJ/kg281.2 286.5 291.5 296.3 300.9 305.3 309.6 313.7 Pressure ratio 15.9515.58 15.21 14.84 14.50 14.16 13.84 13.53 Refrigerant mass flow kg/hr25.6 25.1 24.7 24.3 23.9 23.6 23.3 22.9 Compressor discharge temperature° C. 137.6 140.0 142.2 144.4 146.6 148.7 150.8 152.8 Evaporator inletpressure bar 1.28 1.37 1.47 1.58 1.68 1.80 1.91 2.02 Condenser inletpressure bar 19.9 21.0 22.1 23.1 24.1 25.1 26.2 27.2 Evaporator inlettemperature ° C. −35.0 −35.9 −36.7 −37.7 −38.6 −39.4 −40.3 −41.1Evaporator dewpoint ° C. −24.8 −24.2 −23.6 −23.1 −22.6 −22.2 −21.8 −21.5Evaporator exit gas temperature ° C. −19.8 −19.2 −18.6 −18.1 −17.6 −17.2−16.8 −16.5 Evaporator mean temperature ° C. −29.9 −30.0 −30.2 −30.4−30.6 −30.8 −31.1 −31.3 Evaporator glide (out-in) K 10.2 11.7 13.2 14.616.0 17.3 18.5 19.7 Compressor suction pressure bar 1.25 1.35 1.45 1.561.66 1.78 1.89 2.01 Compressor discharge pressure bar 19.9 21.0 22.123.1 24.1 25.1 26.2 27.2 Suction line pressure drop Pa/m 164 151 139 129120 112 105 98 Pressure drop relative to reference 56.1% 51.6% 47.6%44.1% 41.0% 38.3% 35.8% 33.6% Condenser dew point ° C. 59.8 59.9 59.959.8 59.6 59.3 59.0 58.6 Condenser bubble point ° C. 30.8 29.7 28.7 27.927.2 26.6 26.0 25.6 Condenser exit liquid temperature ° C. 29.8 28.727.7 26.9 26.2 25.6 25.0 24.6 Condenser mean temperature ° C. 45.3 44.844.3 43.8 43.4 42.9 42.5 42.1 Condenser glide (in-out) K 29.0 30.2 31.131.9 32.4 32.7 32.9 33.0

TABLE 25 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 0-14% R-744 and 30%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

0/30/70 2/30/68 4/30/66 6/30/64 8/30/62 10/30/60 12/30/58 14/30/56 COP(heating) 2.00 2.06 2.10 2.13 2.16 2.18 2.19 2.21 COP relative toReference 94.9% 97.5% 99.5% 101.0% 102.3% 103.3% 104.1% 104.7%Volumetric heating capacity at suction kJ/m3 688 766 848 932 1020 11121206 1303 Capacity relative to Reference 78.3% 87.2% 96.5% 106.1% 116.1%126.6% 137.3% 148.3% Critical temperature ° C. 108.11 104.40 100.9097.60 94.48 91.51 88.70 86.03 Critical pressure bar 36.81 37.44 38.0838.73 39.38 40.03 40.69 41.35 Condenser enthalpy change kJ/kg 215.6227.8 238.5 247.8 256.0 263.3 270.0 276.2 Pressure ratio 17.21 17.3517.35 17.24 17.03 16.76 16.45 16.11 Refrigerant mass flow kg/hr 33.431.6 30.2 29.1 28.1 27.3 26.7 26.1 Compressor discharge temperature ° C.113.1 117.0 120.6 123.9 127.0 129.8 132.5 135.0 Evaporator inletpressure bar 0.73 0.77 0.83 0.89 0.96 1.03 1.12 1.20 Condenser inletpressure bar 11.3 12.4 13.5 14.5 15.6 16.7 17.8 18.9 Evaporator inlettemperature ° C. −29.1 −29.7 −30.4 −31.0 −31.7 −32.4 −33.2 −34.0Evaporator dewpoint ° C. −30.0 −29.5 −28.9 −28.3 −27.6 −26.9 −26.2 −25.5Evaporator exit gas temperature ° C. −25.0 −24.5 −23.9 −23.3 −22.6 −21.9−21.2 −20.5 Evaporator mean temperature ° C. −29.6 −29.6 −29.6 −29.6−29.6 −29.7 −29.7 −29.8 Evaporator glide (out-in) K −0.8 0.2 1.5 2.8 4.15.6 7.0 8.5 Compressor suction pressure bar 0.66 0.71 0.78 0.84 0.921.00 1.08 1.17 Compressor discharge pressure bar 11.3 12.4 13.5 14.515.6 16.7 17.8 18.9 Suction line pressure drop Pa/m 405 349 305 270 240216 195 178 Pressure drop relative to reference 138.8% 119.6% 104.5%92.3% 82.3% 73.9% 66.9% 60.9% Condenser dew point ° C. 53.0 54.5 55.856.8 57.7 58.4 58.9 59.3 Condenser bubble point ° C. 52.7 47.8 43.8 40.637.9 35.7 33.9 32.4 Condenser exit liquid temperature ° C. 51.7 46.842.8 39.6 36.9 34.7 32.9 31.4 Condenser mean temperature ° C. 52.8 51.149.8 48.7 47.8 47.1 46.4 45.8 Condenser glide (in-out) K 0.3 6.7 11.916.3 19.8 22.7 25.0 26.9

TABLE 26 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 16-30% R-744 and 30%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

16/30/54 18/30/52 20/30/50 22/30/48 24/30/46 26/30/44 28/30/42 30/30/40COP (heating) 2.22 2.23 2.24 2.24 2.25 2.25 2.25 2.25 COP relative toReference 105.3% 105.7% 106.1% 106.4% 106.6% 106.7% 106.8% 106.8%Volumetric heating capacity at suction kJ/m3 1403 1505 1610 1716 18231932 2043 2155 Capacity relative to Reference 159.7% 171.3% 183.2%195.3% 207.5% 219.9% 232.5% 245.2% Critical temperature ° C. 83.49 81.0778.76 76.56 74.45 72.44 70.51 68.66 Critical pressure bar 42.02 42.6943.36 44.03 44.71 45.38 46.06 46.74 Condenser enthalpy change kJ/kg281.9 287.2 292.2 297.0 301.6 306.1 310.4 314.5 Pressure ratio 15.7515.39 15.03 14.68 14.33 14.00 13.69 13.38 Refrigerant mass flow kg/hr25.5 25.1 24.6 24.2 23.9 23.5 23.2 22.9 Compressor discharge temperature° C. 137.4 139.7 142.0 144.2 146.3 148.4 150.5 152.5 Evaporator inletpressure bar 1.29 1.39 1.49 1.59 1.70 1.81 1.92 2.04 Condenser inletpressure bar 19.9 21.0 22.0 23.0 24.1 25.1 26.1 27.1 Evaporator inlettemperature ° C. −34.9 −35.7 −36.6 −37.5 −38.3 −39.2 −40.0 −40.9Evaporator dewpoint ° C. −24.9 −24.3 −23.7 −23.2 −22.7 −22.3 −21.9 −21.6Evaporator exit gas temperature ° C. −19.9 −19.3 −18.7 −18.2 −17.7 −17.3−16.9 −16.6 Evaporator mean temperature ° C. −29.9 −30.0 −30.1 −30.3−30.5 −30.7 −31.0 −31.2 Evaporator glide (out-in) K 10.0 11.5 12.9 14.315.6 16.9 18.1 19.3 Compressor suction pressure bar 1.26 1.36 1.46 1.571.68 1.79 1.91 2.02 Compressor discharge pressure bar 19.9 21.0 22.023.0 24.1 25.1 26.1 27.1 Suction line pressure drop Pa/m 163 149 138 128119 111 104 98 Pressure drop relative to reference 55.7% 51.2% 47.2%43.8% 40.7% 38.0% 35.6% 33.4% Condenser dew point ° C. 59.5 59.6 59.659.6 59.4 59.1 58.8 58.4 Condenser bubble point ° C. 31.1 29.9 29.0 28.227.4 26.8 26.3 25.8 Condenser exit liquid temperature ° C. 30.1 28.928.0 27.2 26.4 25.8 25.3 24.8 Condenser mean temperature ° C. 45.3 44.844.3 43.9 43.4 43.0 42.5 42.1 Condenser glide (in-out) K 28.5 29.7 30.731.4 31.9 32.3 32.6 32.7

TABLE 27 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 0-14% R-744 and 35%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

0/35/65 2/35/63 4/35/61 6/35/59 8/35/57 10/35/55 12/35/53 14/35/51 COP(heating) 2.00 2.06 2.10 2.13 2.16 2.18 2.19 2.21 COP relative toReference 94.9% 97.5% 99.5% 101.0% 102.2% 103.2% 104.1% 104.7%Volumetric heating capacity at suction kJ/m3 699 777 858 942 1030 11211215 1312 Capacity relative to Reference 79.5% 88.4% 97.6% 107.2% 117.2%127.6% 138.3% 149.3% Critical temperature ° C. 107.83 104.16 100.7097.43 94.33 91.40 88.61 85.96 Critical pressure bar 36.79 37.41 38.0338.66 39.30 39.94 40.58 41.23 Condenser enthalpy change kJ/kg 216.6228.7 239.2 248.5 256.7 264.1 270.8 276.9 Pressure ratio 17.00 17.1217.12 17.01 16.81 16.55 16.24 15.91 Refrigerant mass flow kg/hr 33.231.5 30.1 29.0 28.0 27.3 26.6 26.0 Compressor discharge temperature ° C.113.2 117.0 120.5 123.8 126.9 129.7 132.3 134.9 Evaporator inletpressure bar 0.74 0.78 0.84 0.90 0.97 1.05 1.13 1.21 Condenser inletpressure bar 11.4 12.4 13.5 14.6 15.6 16.7 17.8 18.8 Evaporator inlettemperature ° C. −29.2 −29.7 −30.4 −31.0 −31.7 −32.4 −33.2 −33.9Evaporator dewpoint ° C. −30.0 −29.5 −28.9 −28.3 −27.6 −26.9 −26.2 −25.6Evaporator exit gas temperature ° C. −25.0 −24.5 −23.9 −23.3 −22.6 −21.9−21.2 −20.6 Evaporator mean temperature ° C. −29.6 −29.6 −29.6 −29.6−29.7 −29.7 −29.7 −29.8 Evaporator glide (out-in) K −0.8 0.3 1.4 2.7 4.15.5 6.9 8.4 Compressor suction pressure bar 0.67 0.73 0.79 0.86 0.931.01 1.09 1.18 Compressor discharge pressure bar 11.4 12.4 13.5 14.615.6 16.7 17.8 18.8 Suction line pressure drop Pa/m 398 344 301 266 238214 194 176 Pressure drop relative to reference 136.2% 117.6% 103.0%91.1% 81.4% 73.2% 66.3% 60.3% Condenser dew point ° C. 52.9 54.4 55.656.7 57.5 58.2 58.7 59.1 Condenser bubble point ° C. 52.7 47.9 44.0 40.838.2 36.0 34.2 32.6 Condenser exit liquid temperature ° C. 51.7 46.943.0 39.8 37.2 35.0 33.2 31.6 Condenser mean temperature ° C. 52.8 51.149.8 48.7 47.8 47.1 46.4 45.9 Condenser glide (in-out) K 0.3 6.5 11.615.9 19.4 22.2 24.6 26.5

TABLE 28 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 16-30% R-744 and 35%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

16/35/49 18/35/47 20/35/45 22/35/43 24/35/41 26/35/39 28/35/37 30/35/35COP (heating) 2.22 2.23 2.24 2.24 2.25 2.25 2.25 2.25 COP relative toReference 105.3% 105.7% 106.1% 106.4% 106.6% 106.8% 106.9% 106.9%Volumetric heating capacity at suction kJ/m3 1412 1514 1618 1724 18321941 2051 2163 Capacity relative to Reference 160.7% 172.3% 184.1%196.2% 208.4% 220.9% 233.5% 246.2% Critical temperature ° C. 83.44 81.0478.75 76.56 74.47 72.46 70.55 68.71 Critical pressure bar 41.88 42.5343.19 43.85 44.51 45.18 45.85 46.52 Condenser enthalpy change kJ/kg282.6 288.0 293.0 297.9 302.5 306.9 311.2 315.4 Pressure ratio 15.5615.21 14.86 14.52 14.18 13.86 13.55 13.25 Refrigerant mass flow kg/hr25.5 25.0 24.6 24.2 23.8 23.5 23.1 22.8 Compressor discharge temperature° C. 137.3 139.6 141.8 143.9 146.1 148.1 150.2 152.2 Evaporator inletpressure bar 1.31 1.40 1.50 1.60 1.71 1.82 1.94 2.05 Condenser inletpressure bar 19.9 20.9 22.0 23.0 24.0 25.0 26.0 27.0 Evaporator inlettemperature ° C. −34.8 −35.6 −36.4 −37.3 −38.1 −39.0 −39.8 −40.6Evaporator dewpoint ° C. −24.9 −24.3 −23.8 −23.3 −22.8 −22.4 −22.0 −21.7Evaporator exit gas temperature ° C. −19.9 −19.3 −18.8 −18.3 −17.8 −17.4−17.0 −16.7 Evaporator mean temperature ° C. −29.9 −30.0 −30.1 −30.3−30.5 −30.7 −30.9 −31.2 Evaporator glide (out-in) K 9.8 11.2 12.6 14.015.3 16.6 17.8 18.9 Compressor suction pressure bar 1.28 1.38 1.48 1.581.69 1.80 1.92 2.04 Compressor discharge pressure bar 19.9 20.9 22.023.0 24.0 25.0 26.0 27.0 Suction line pressure drop Pa/m 161 148 137 127118 110 103 97 Pressure drop relative to reference 55.2% 50.8% 46.9%43.5% 40.5% 37.8% 35.4% 33.2% Condenser dew point ° C. 59.3 59.4 59.559.4 59.2 59.0 58.7 58.3 Condenser bubble point ° C. 31.3 30.2 29.2 28.427.7 27.0 26.5 26.0 Condenser exit liquid temperature ° C. 30.3 29.228.2 27.4 26.7 26.0 25.5 25.0 Condenser mean temperature ° C. 45.3 44.844.3 43.9 43.4 43.0 42.6 42.2 Condenser glide (in-out) K 28.0 29.3 30.231.0 31.6 32.0 32.2 32.3

TABLE 29 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 0-14% R-744 and 40%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

0/40/60 2/40/58 4/40/56 6/40/54 8/40/52 10/40/50 12/40/48 14/40/46 COP(heating) 2.00 2.06 2.10 2.13 2.16 2.18 2.19 2.21 COP relative toReference 95.0% 97.5% 99.5% 101.0% 102.2% 103.2% 104.0% 104.7%Volumetric heating capacity at suction kJ/m3 709 787 867 951 1039 11301223 1320 Capacity relative to Reference 80.7% 89.5% 98.7% 108.3% 118.2%128.6% 139.2% 150.2% Critical temperature ° C. 107.55 103.92 100.5097.26 94.19 91.28 88.52 85.89 Critical pressure bar 36.76 37.36 37.9738.58 39.20 39.83 40.46 41.09 Condenser enthalpy change kJ/kg 217.7229.6 240.1 249.3 257.5 264.8 271.6 277.7 Pressure ratio 16.80 16.9116.91 16.80 16.61 16.35 16.05 15.73 Refrigerant mass flow kg/hr 33.131.4 30.0 28.9 28.0 27.2 26.5 25.9 Compressor discharge temperature ° C.113.3 117.0 120.5 123.8 126.8 129.6 132.2 134.7 Evaporator inletpressure bar 0.75 0.80 0.85 0.91 0.98 1.06 1.14 1.23 Condenser inletpressure bar 11.5 12.5 13.5 14.6 15.7 16.7 17.8 18.8 Evaporator inlettemperature ° C. −29.2 −29.8 −30.4 −31.0 −31.7 −32.3 −33.1 −33.9Evaporator dewpoint ° C. −29.9 −29.5 −28.9 −28.3 −27.7 −27.0 −26.3 −25.7Evaporator exit gas temperature ° C. −24.9 −24.5 −23.9 −23.3 −22.7 −22.0−21.3 −20.7 Evaporator mean temperature ° C. −29.6 −29.6 −29.6 −29.6−29.7 −29.7 −29.7 −29.8 Evaporator glide (out-in) K −0.8 0.3 1.4 2.7 4.05.4 6.8 8.2 Compressor suction pressure bar 0.68 0.74 0.80 0.87 0.941.02 1.11 1.20 Compressor discharge pressure bar 11.5 12.5 13.5 14.615.7 16.7 17.8 18.8 Suction line pressure drop Pa/m 391 338 297 263 235212 192 175 Pressure drop relative to reference 133.8% 115.8% 101.6%90.0% 80.5% 72.5% 65.7% 59.8% Condenser dew point ° C. 52.9 54.3 55.556.5 57.4 58.0 58.5 58.9 Condenser bubble point ° C. 52.6 48.0 44.1 41.038.4 36.2 34.4 32.9 Condenser exit liquid temperature ° C. 51.6 47.043.1 40.0 37.4 35.2 33.4 31.9 Condenser mean temperature ° C. 52.8 51.149.8 48.8 47.9 47.1 46.5 45.9 Condenser glide (in-out) K 0.3 6.3 11.415.5 19.0 21.8 24.1 26.0

TABLE 30 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 16-30% R-744 and 40%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

16/40/44 18/40/42 20/40/40 22/40/38 24/40/36 26/40/34 28/40/32 30/40/30COP (heating) 2.22 2.23 2.24 2.24 2.25 2.25 2.26 2.26 COP relative toReference 105.3% 105.8% 106.1% 106.4% 106.7% 106.8% 107.0% 107.0%Volumetric heating capacity at suction kJ/m3 1420 1521 1625 1731 18391948 2059 2171 Capacity relative to Reference 161.6% 173.1% 185.0%197.0% 209.3% 221.7% 234.3% 247.0% Critical temperature ° C. 83.39 81.0178.73 76.56 74.48 72.49 70.58 68.75 Critical pressure bar 41.73 42.3743.02 43.67 44.32 44.97 45.63 46.29 Condenser enthalpy change kJ/kg283.5 288.8 293.9 298.8 303.4 307.9 312.2 316.4 Pressure ratio 15.3915.05 14.71 14.37 14.04 13.73 13.42 13.13 Refrigerant mass flow kg/hr25.4 24.9 24.5 24.1 23.7 23.4 23.1 22.8 Compressor discharge temperature° C. 137.1 139.4 141.6 143.8 145.9 147.9 149.9 151.9 Evaporator inletpressure bar 1.32 1.41 1.51 1.62 1.72 1.84 1.95 2.07 Condenser inletpressure bar 19.9 20.9 21.9 22.9 23.9 24.9 25.9 26.9 Evaporator inlettemperature ° C. −34.7 −35.5 −36.3 −37.1 −38.0 −38.8 −39.6 −40.4Evaporator dewpoint ° C. −25.0 −24.4 −23.9 −23.4 −22.9 −22.5 −22.1 −21.8Evaporator exit gas temperature ° C. −20.0 −19.4 −18.9 −18.4 −17.9 −17.5−17.1 −16.8 Evaporator mean temperature ° C. −29.8 −30.0 −30.1 −30.3−30.4 −30.6 −30.9 −31.1 Evaporator glide (out-in) K 9.6 11.0 12.4 13.715.0 16.3 17.4 18.5 Compressor suction pressure bar 1.29 1.39 1.49 1.601.70 1.82 1.93 2.05 Compressor discharge pressure bar 19.9 20.9 21.922.9 23.9 24.9 25.9 26.9 Suction line pressure drop Pa/m 160 147 136 126117 110 103 96 Pressure drop relative to reference 54.8% 50.4% 46.6%43.2% 40.2% 37.5% 35.1% 33.0% Condenser dew point ° C. 59.1 59.3 59.359.2 59.1 58.9 58.6 58.2 Condenser bubble point ° C. 31.5 30.4 29.5 28.627.9 27.2 26.7 26.2 Condenser exit liquid temperature ° C. 30.5 29.428.5 27.6 26.9 26.2 25.7 25.2 Condenser mean temperature ° C. 45.3 44.844.4 43.9 43.5 43.0 42.6 42.2 Condenser glide (in-out) K 27.6 28.8 29.830.6 31.2 31.6 31.9 32.0

TABLE 31 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 0-14% R-744 and 45%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

0/45/55 2/45/53 4/45/51 6/45/49 8/45/47 10/45/45 12/45/43 14/45/41 COP(heating) 2.01 2.06 2.10 2.13 2.15 2.18 2.19 2.21 COP relative toReference 95.1% 97.5% 99.5% 101.0% 102.2% 103.2% 104.0% 104.7%Volumetric heating capacity at suction kJ/m3 719 796 876 960 1047 11381231 1328 Capacity relative to Reference 81.8% 90.6% 99.7% 109.3% 119.2%129.5% 140.1% 151.1% Critical temperature ° C. 107.28 103.69 100.3097.09 94.06 91.17 88.43 85.83 Critical pressure bar 36.72 37.31 37.9038.49 39.10 39.71 40.33 40.95 Condenser enthalpy change kJ/kg 218.8230.6 241.0 250.1 258.3 265.7 272.4 278.6 Pressure ratio 16.61 16.7116.71 16.60 16.41 16.16 15.87 15.56 Refrigerant mass flow kg/hr 32.931.2 29.9 28.8 27.9 27.1 26.4 25.8 Compressor discharge temperature ° C.113.4 117.1 120.6 123.8 126.8 129.5 132.1 134.6 Evaporator inletpressure bar 0.76 0.81 0.86 0.93 0.99 1.07 1.15 1.24 Condenser inletpressure bar 11.5 12.5 13.6 14.6 15.7 16.7 17.7 18.8 Evaporator inlettemperature ° C. −29.2 −29.8 −30.3 −31.0 −31.6 −32.3 −33.0 −33.8Evaporator dewpoint ° C. −29.9 −29.5 −29.0 −28.3 −27.7 −27.0 −26.4 −25.7Evaporator exit gas temperature ° C. −24.9 −24.5 −24.0 −23.3 −22.7 −22.0−21.4 −20.7 Evaporator mean temperature ° C. −29.6 −29.6 −29.6 −29.7−29.7 −29.7 −29.7 −29.8 Evaporator glide (out-in) K −0.8 0.3 1.4 2.6 3.95.3 6.6 8.0 Compressor suction pressure bar 0.69 0.75 0.81 0.88 0.951.03 1.12 1.21 Compressor discharge pressure bar 11.5 12.5 13.6 14.615.7 16.7 17.7 18.8 Suction line pressure drop Pa/m 384 333 293 260 233210 190 173 Pressure drop relative to reference 131.4% 114.1% 100.3%89.0% 79.6% 71.8% 65.1% 59.4% Condenser dew point ° C. 52.8 54.2 55.456.4 57.2 57.8 58.3 58.7 Condenser bubble point ° C. 52.6 48.0 44.3 41.238.6 36.4 34.6 33.1 Condenser exit liquid temperature ° C. 51.6 47.043.3 40.2 37.6 35.4 33.6 32.1 Condenser mean temperature ° C. 52.7 51.149.8 48.8 47.9 47.1 46.5 45.9 Condenser glide (in-out) K 0.2 6.1 11.115.2 18.6 21.4 23.7 25.6

TABLE 32 Theoretical Performance Data of SelectedR-744/R-1243zf/R-1234ze(E) blends containing 16-30% R-744 and 45%R-1243zf Composition CO₂/R-1243zf/R-1234ze(E) % by weight 

16/45/39 18/45/37 20/45/35 22/45/33 24/45/31 26/45/29 28/45/27 30/45/25COP (heating) 2.22 2.23 2.24 2.25 2.25 2.25 2.26 2.26 COP relative toReference 105.3% 105.8% 106.2% 106.5% 106.7% 106.9% 107.0% 107.1%Volumetric heating capacity at suction kJ/m3 1427 1528 1632 1738 18451954 2065 2177 Capacity relative to Reference 162.4% 173.9% 185.7%197.8% 210.0% 222.4% 235.0% 247.7% Critical temperature ° C. 83.34 80.9878.72 76.56 74.49 72.51 70.62 68.80 Critical pressure bar 41.58 42.2142.84 43.48 44.12 44.76 45.41 46.05 Condenser enthalpy change kJ/kg284.4 289.8 294.9 299.8 304.4 308.9 313.3 317.5 Pressure ratio 15.2314.90 14.56 14.23 13.91 13.60 13.30 13.01 Refrigerant mass flow kg/hr25.3 24.8 24.4 24.0 23.7 23.3 23.0 22.7 Compressor discharge temperature° C. 137.0 139.3 141.5 143.6 145.7 147.7 149.7 151.7 Evaporator inletpressure bar 1.33 1.42 1.52 1.63 1.73 1.85 1.96 2.08 Condenser inletpressure bar 19.8 20.8 21.9 22.9 23.9 24.9 25.8 26.8 Evaporator inlettemperature ° C. −34.6 −35.4 −36.2 −37.0 −37.8 −38.6 −39.4 −40.1Evaporator dewpoint ° C. −25.1 −24.5 −24.0 −23.5 −23.0 −22.6 −22.2 −21.9Evaporator exit gas temperature ° C. −20.1 −19.5 −19.0 −18.5 −18.0 −17.6−17.2 −16.9 Evaporator mean temperature ° C. −29.8 −29.9 −30.1 −30.2−30.4 −30.6 −30.8 −31.0 Evaporator glide (out-in) K 9.4 10.8 12.2 13.514.8 16.0 17.1 18.2 Compressor suction pressure bar 1.30 1.40 1.50 1.611.71 1.83 1.94 2.06 Compressor discharge pressure bar 19.8 20.8 21.922.9 23.9 24.9 25.8 26.8 Suction line pressure drop Pa/m 159 146 135 125117 109 102 96 Pressure drop relative to reference 54.4% 50.1% 46.3%42.9% 40.0% 37.3% 35.0% 32.8% Condenser dew point ° C. 59.0 59.1 59.159.1 58.9 58.7 58.5 58.2 Condenser bubble point ° C. 31.8 30.6 29.7 28.828.1 27.4 26.9 26.4 Condenser exit liquid temperature ° C. 30.8 29.628.7 27.8 27.1 26.4 25.9 25.4 Condenser mean temperature ° C. 45.4 44.944.4 43.9 43.5 43.1 42.7 42.3 Condenser glide (in-out) K 27.2 28.5 29.530.3 30.9 31.3 31.6 31.8

TABLE 33 Theoretical Performance Data of Selected R-744/R-1234ze(E)blends containing 0-14% R-744 Composition CO₂/R-1234ze(E) % by weight 

0/100 2/98 4/96 6/94 8/92 10/90 12/88 14/86 COP (heating) 1.99 2.05 2.102.14 2.16 2.18 2.20 2.21 COP (heating) relative to Reference 94.4% 97.4%99.6% 101.3% 102.5% 103.5% 104.3% 104.9% Volumetric heating capacity atsuction kJ/m3 615 695 778 864 953 1046 1141 1239 Capacity relative toReference 70.0% 79.1% 88.6% 98.3% 108.5% 119.0% 129.8% 141.0% Criticaltemperature ° C. 109.89 105.93 102.20 98.69 95.38 92.25 89.29 86.48Critical pressure bar 36.57 37.34 38.10 38.87 39.63 40.40 41.16 41.92Condenser enthalpy change kJ/kg 210.2 223.7 235.1 244.8 253.2 260.5267.2 273.2 Pressure ratio 18.75 18.99 19.05 18.95 18.71 18.39 18.0017.58 Refrigerant mass flow kg/hr 34.2 32.2 30.6 29.4 28.4 27.6 27.026.4 Compressor discharge temperature ° C. 112.8 117.1 121.1 124.7 127.9131.0 133.8 136.5 Evaporator inlet pressure bar 0.65 0.69 0.74 0.80 0.870.95 1.03 1.11 Condenser inlet pressure bar 10.7 11.9 13.1 14.3 15.516.7 17.8 19.0 Evaporator inlet temperature ° C. −28.9 −29.6 −30.3 −31.1−31.9 −32.7 −33.6 −34.5 Evaporator dewpoint ° C. −30.3 −29.7 −29.0 −28.3−27.5 −26.6 −25.8 −25.1 Evaporator exit gas temperature ° C. −25.3 −24.7−24.0 −23.3 −22.5 −21.6 −20.8 −20.1 Evaporator mean temperature ° C.−29.6 −29.7 −29.7 −29.7 −29.7 −29.7 −29.7 −29.8 Evaporator glide(out-in) K −1.3 −0.1 1.3 2.8 4.4 6.0 7.7 9.4 Compressor suction pressurebar 0.57 0.63 0.69 0.75 0.83 0.91 0.99 1.08 Compressor dischargepressure bar 10.7 11.9 13.1 14.3 15.5 16.7 17.8 19.0 Suction linepressure drop Pa/m 462 390 336 294 259 231 208 189 Pressure droprelative to reference 158.3% 133.6% 115.0% 100.5% 88.8% 79.2% 71.3%64.6% Condenser dew point ° C. 53.1 55.1 56.7 58.1 59.2 60.0 60.5 60.9Condenser bubble point ° C. 53.0 47.1 42.6 38.9 36.1 33.8 31.9 30.4Condenser exit liquid temperature ° C. 52.0 46.1 41.6 37.9 35.1 32.830.9 29.4 Condenser mean temperature ° C. 53.1 51.1 49.7 48.5 47.6 46.946.2 45.7 Condenser glide (in-out) K 0.1 7.9 14.2 19.1 23.1 26.2 28.630.6

TABLE 34 Theoretical Performance Data of Selected R-744/R-1234ze(E)blends containing 16-30% R-744 Composition CO₂/R-1234ze(E) % by weight 

16/84 18/82 20/80 22/78 24/76 26/74 28/72 30/70 COP (heating) 2.22 2.232.23 2.24 2.24 2.24 2.24 2.24 COP (heating) relative to Reference 105.4%105.7% 106.0% 106.2% 106.3% 106.3% 106.3% 106.2% Volumetric heatingcapacity at suction kJ/m3 1339 1441 1545 1650 1756 1862 1969 2076Capacity relative to Reference 152.4% 164.0% 175.8% 187.7% 199.8% 211.9%224.1% 236.3% Critical temperature ° C. 83.81 81.28 78.87 76.57 74.3872.28 70.28 68.37 Critical pressure bar 42.68 43.44 44.20 44.96 45.7246.47 47.23 47.98 Condenser enthalpy change kJ/kg 278.7 283.9 288.9293.6 298.1 302.5 306.8 311.0 Pressure ratio 17.15 16.72 16.29 15.8815.49 15.12 14.77 14.44 Refrigerant mass flow kg/hr 25.8 25.4 24.9 24.524.2 23.8 23.5 23.1 Compressor discharge temperature ° C. 139.0 141.4143.8 146.1 148.4 150.6 152.9 155.1 Evaporator inlet pressure bar 1.201.29 1.39 1.49 1.60 1.70 1.81 1.92 Condenser inlet pressure bar 20.121.2 22.3 23.3 24.4 25.4 26.5 27.5 Evaporator inlet temperature ° C.−35.5 −36.5 −37.6 −38.7 −39.7 −40.8 −41.9 −42.9 Evaporator dewpoint ° C.−24.4 −23.7 −23.1 −22.5 −22.0 −21.6 −21.2 −20.9 Evaporator exit gastemperature ° C. −19.4 −18.7 −18.1 −17.5 −17.0 −16.6 −16.2 −15.9Evaporator mean temperature ° C. −29.9 −30.1 −30.3 −30.6 −30.9 −31.2−31.5 −31.9 Evaporator glide (out-in) K 11.2 12.9 14.5 16.2 17.7 19.220.7 22.0 Compressor suction pressure bar 1.17 1.27 1.37 1.47 1.57 1.681.79 1.90 Compressor discharge pressure bar 20.1 21.2 22.3 23.3 24.425.4 26.5 27.5 Suction line pressure drop Pa/m 172 157 145 134 125 116109 102 Pressure drop relative to reference 58.8% 53.9% 49.7% 45.9%42.7% 39.8% 37.2% 35.0% Condenser dew point ° C. 61.2 61.2 61.2 61.060.8 60.4 60.0 59.5 Condenser bubble point ° C. 29.1 28.0 27.1 26.3 25.725.1 24.6 24.1 Condenser exit liquid temperature ° C. 28.1 27.0 26.125.3 24.7 24.1 23.6 23.1 Condenser mean temperature ° C. 45.1 44.6 44.143.7 43.2 42.7 42.3 41.8 Condenser glide (in-out) K 32.1 33.2 34.1 34.735.1 35.3 35.4 35.3

In summary, the invention provides new compositions that exhibit asurprising combination of advantageous properties including goodrefrigeration performance, low flammability, low GWP, and/or miscibilitywith lubricants compared to existing refrigerants such as R-134a and theproposed refrigerant R-1234yf.

The invention is defined by the following claims.

What is claimed is:
 1. A heat transfer composition consistingessentially of: (i) a first component selected from about 10 to about95% by weight R-1234ze(E); (ii) from about 2 to about 30% by weightR-744; and (iii) from about 3 to about 60% by weight of a thirdcomponent selected from R-1234yf or R-1243zf; wherein the compositionhas a critical temperature of 70° C. or greater.
 2. A compositionaccording to claim 1 comprising at least about 15% by weightR-1234ze(E).
 3. A composition according to claim 1 comprising from about4 to about 30% R-744 by weight.
 4. A composition according to claim 1comprising up to about 50% by weight of the third component.
 5. Acomposition according to claim 1 wherein the third component isR-1234yf.
 6. A composition according to claim 5 consisting essentiallyof from about 10 to about 92% R-1234ze(E), from about 4 to about 30% byweight R-744 and from about 4 to about 60% by weight R-1234yf.
 7. Acomposition according to claim 6 consisting essentially of from about 22to about 84% R-1234ze(E), from about 10 to about 28% by weight R-744 andfrom about 6 to about 50% by weight R-1234yf.
 8. A composition accordingto claim 6 consisting essentially of from about 14 to about 86%R-1234ze(E), from about 4 to about 26% by weight R-744 and from about 10to about 60% by weight R-1234yf.
 9. A composition according to claim 1wherein the third component is R-1243zf.
 10. A composition according toclaim 9 consisting essentially of from about 20 to about 92%R-1234ze(E), from about 4 to about 30% by weight R-744 and from about 4to about 50% by weight R-1243zf.
 11. A composition according to claim 10consisting essentially of from about 32 to about 88% R-1234ze(E), fromabout 6 to about 28% by weight R-744 and from about 6 to about 40% byweight R-1243zf.
 12. A composition according to claim 1, wherein thecomposition has a GWP of less than
 1000. 13. A composition according toclaim 1, wherein the composition has a volumetric refrigeration capacitywithin about 15% of an existing refrigerant and the composition isintended to replace the existing refrigerant.
 14. A compositionaccording to claim 1, wherein the composition is less flammable thanR-1234yf alone or R-1243zf alone.
 15. A composition according to claim14, wherein the composition has at least one of: (a) a higher flammablelimit; (b) a higher ignition energy; or (c) a lower flame velocitycompared to R-1234yf alone or R-1243zf alone.
 16. A compositionaccording to claim 1 wherein the composition has a fluorine ratio(F/(F+H)) of from about 0.42 to about 0.7.
 17. A composition accordingto claim 1 wherein the composition is non-flammable.
 18. A compositionaccording to claim 1, wherein the composition has a cycle efficiencywithin about 5% of an existing refrigerant and the composition isintended to replace the existing refrigerant.
 19. A compositionaccording to claim 1, wherein the composition has a compressor dischargetemperature within about 15K of an existing refrigerant and thecomposition is intended to replace the existing refrigerant.
 20. Acomposition comprising a lubricant and the composition according toclaim
 1. 21. A composition according to claim 20, wherein the lubricantis selected from mineral oil, silicone oil, PABs, POEs, PAGs, PAGesters, PVEs, poly (alpha-olefins) and combinations thereof.
 22. Acomposition according to claim 20 further comprising a stabilizer.
 23. Acomposition according to claim 22, wherein the stabilizer is selectedfrom diene-based compounds, phosphates, phenol compounds and epoxides,and mixtures thereof.
 24. A composition comprising a flame retardant andthe composition according to claim
 1. 25. A composition according toclaim 24, wherein the flame retardant is selected from the groupconsisting of tri-(2-chloroethyl)-phosphate, (chloropropyl)phosphate,tri-(2,3-dibromopropyl)-phosphate, tri-(1,3-dichloropropyl)-phosphate,diammonium phosphate, halogenated aromatic compounds, antimony oxide,aluminium trihydrate, polyvinyl chloride, a fluorinated iodocarbon, afluorinated bromo carbon, trifluoro iodomethane, perfluoroalkyl amines,bromo-fluoroalkyl amines and mixtures thereof.
 26. A compositionaccording to claim 1 wherein the composition is a refrigerantcomposition.
 27. A heat transfer device containing the composition ofclaim
 1. 28. A heat transfer device according to claim 27 wherein theheat transfer device is a refrigeration device.
 29. A heat transferdevice according to claim 28 wherein the heat transfer device isselected from group consisting of automotive air conditioning systems,residential air conditioning systems, commercial air conditioningsystems, residential refrigerator systems, residential freezer systems,commercial refrigerator systems, commercial freezer systems, chiller airconditioning systems, chiller refrigeration systems, and commercial orresidential heat pump systems.
 30. A heat transfer device according toclaim 28 wherein the heat transfer device contains a compressor.
 31. Ablowing agent comprising the composition of claim
 1. 32. A foamablecomposition comprising one or more components capable of forming foamand the composition of claim 1, wherein the one or more componentscapable of forming foam are selected from polyurethanes, thermoplasticpolymers and resins, and mixtures thereof.
 33. A foam comprising thecomposition of claim
 1. 34. A sprayable composition comprising materialto be sprayed and a propellant comprising the composition of claim 1.35. A method for cooling an article comprising condensing thecomposition of claim 1 and thereafter evaporating the composition in thevicinity of the article to be cooled.
 36. A method for heating anarticle comprising condensing the composition of claim 1 in the vicinityof the article to be heated and thereafter evaporating the composition.37. A method for extracting a substance from biomass comprisingcontacting the biomass with a solvent comprising the composition ofclaim 1, and separating the substance from the solvent.
 38. A method ofcleaning an article comprising contacting the article with a solventcomprising the composition of claim
 1. 39. A method of extracting amaterial from an aqueous solution comprising contacting the aqueoussolution with a solvent comprising the composition of claim 1, andseparating the material from the solvent.
 40. A method for extracting amaterial from a particulate solid matrix comprising contacting theparticulate solid matrix with a solvent comprising the composition ofclaim 1, and separating the material from the solvent.
 41. A mechanicalpower generation device containing the composition of claim
 1. 42. Amechanical power generating device according to claim 41 wherein themechanical power generating device is adapted to use a Rankine Cycle ormodification thereof to generate work from heat.
 43. A method ofretrofitting a heat transfer device comprising the step of removing anexisting heat transfer fluid, and introducing the composition ofclaim
 1. 44. A method of claim 43 wherein the heat transfer device is arefrigeration device.
 45. A method according to claim 44 wherein theheat transfer device is an air conditioning system.
 46. A method forreducing the environmental impact arising from the operation of a devicecomprising an existing compound or composition, the method comprisingreplacing at least partially the existing compound or composition withthe composition of claim
 1. 47. A method according to claim 46 whereinthe device is selected from a heat transfer device, a blowing agent, afoamable composition, a sprayable composition, a solvent or a mechanicalpower generation device.
 48. A method according to claim 47 wherein thedevice is a heat transfer device.
 49. A method for generating greenhousegas emission credit comprising (i) replacing an existing compound orcomposition with the composition of claim 1, wherein the composition hasa lower GWP than the existing compound or composition; and (ii)obtaining greenhouse gas emission credit for said replacing step.
 50. Amethod of claim 49 wherein the use of the composition results in atleast one of a lower Total Equivalent Warming Impact, or a lowerLife-Cycle Carbon Production than is attained by use of the existingcompound or composition.
 51. A method of claim 49 carried out on aproduct from at least one field of air-conditioning, refrigeration, heattransfer, blowing agents, aerosols or sprayable propellants, gaseousdielectrics, cryosurgery, veterinary procedures, dental procedures, fireextinguishing, flame suppression, solvents, cleaners, air horns, pelletguns, topical anesthetics, or expansion applications.
 52. A methodaccording to claim 49 wherein the existing compound or composition is aheat transfer composition.
 53. A method according to claim 52 whereinthe heat transfer composition is a refrigerant selected from R-134a,R-1234yf, R-152a, R-404A, R-410A, R-507, R-407A, R-407B, R-407D, R-407Eand R-407F.
 54. A method for preparing the composition of claim 1, thecomposition comprising R-134a, the method comprising introducingR-1234ze(E), R-744, and the third component into a heat transfer devicecontaining an existing heat transfer fluid which is R-134a.
 55. A methodaccording to claim 54 further comprising removing at least some of theexisting R-134a from the heat transfer device before introducing theR-1234ze(E), R-744, and the third component.